JPH04502632A - Improved nylon formulations for blow molding - 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] Improved nylon formulations for blow molding Background of the invention Semi-crystalline polyamides are used in many applications requiring high solvent resistance and good properties at high temperatures. Widely used in applications. This is usually processed by injection molding, but it is hollow and injection molded. There are many parts for automobiles and other systems that are very difficult and expensive to manufacture with molds. . If the polymer system has suitable melt strength and viscosity, many such parts Of course, it can be manufactured by blow molding. Unfortunately commonly used in injection molding The number average molecular weight of polyamide is generally 10,000-25,000, and extrusion blowing It is too low to make the polymer suitable for molding. Manufactured from injection moldable polyamide It is desirable to have a blended blow moldable polyamide blend.

Polyamide blends with improved toughness are needed in many applications.

The prior art describes various methods for modifying polyamides with toughening agents. the Such tougheners include low modulus ethylene colloids containing small amounts of carboxyl or anhydride functionality. Contains polymers. Other reinforcing agents include ethylene acid neutralized with metal cations. Polymers included (Epstein U.

S, Patent 4,174,358 or Murch U, S, Patent 3.845.163 The combination of polyamide and such reinforcing agents makes it tough and injection moldable. This is a unique combination suitable for extrusion and extrusion. However, these combinations are It has a viscosity lower than the optimum viscosity and a melt strength lower than the optimum melt strength for use in the mold. Ru.

In the present invention, a coupling compound that preferentially reacts with polyamide to increase its molecular weight is used. Adding a small amount of anhydride-rich polymer to act as a gluing or crosslinking agent substantially increases the melt viscosity of blends of polyamide and the aforementioned reinforcing polymers. . At the same time, such polymers with high anhydride content also react with acid groups in the reinforcing polymer. Accordingly, its viscosity also increases. diisocyanates, epoxides, melamine, etc. Other coupling or crosslinking agents can be used to replace the carboxylic acid in the reinforced resin instead of the polyamide. tends to react preferentially with the group and is therefore sufficient for the purpose desired in this case. not achieved. Thus, by adding polymers with high anhydride content, , extrusion blow molding of semi-crystalline polyamide to form hollow, rigid parts of various shapes It becomes easier to do.

The formulation is basically: a) 99-65 parts by weight of a semi-crystalline polymer with a number average molecular weight of 10,000-25,000; Riamide: b) 1-30 parts by weight 1) at least one α-ole, partially or completely neutralized with metal cations; Ionic copolymer of fins and at least one α,β-unsaturated organic carboxylic acid - or 2) Polyethylene and functional groups containing up to 10% by weight of carboxylic acid or anhydride functional moieties. a mixture of functionalized polyethylene; and C) 0.1-3 parts by weight of male Inic acid anhydride and alpha-olefins such as styrene, ethylene or octadecene and containing at least 15% by weight of anhydride units. Consisting of polymers.

Of course, the amounts of each additive included are relative. For example, the amount of component b) decreases and the amount of component C) must be increased, and if the amount of component b) used is increased. C) can be reduced.

These formulations have high melt strength compared to basic polyamides. This property is Helps form moldable formulations. This formulation is easy to process by extrusion blow molding. , manufacture of hollow parts such as automobile parts for use in containers or under the hood. I can do it.

Detailed description of the invention In the polyamide of the formulations of the present invention) lix resins are well known in the art and have a molecular weight of 10,000-25,000 and is commonly referred to as nylon.

Suitable polyamides include U, S, Patents 2,071,250; 2,071,251: 2,130,523; 2.130,948; 2,241°322; 2.312. 966; 2,512.606; and 3.393.210. be caught. Polyamide resin is a saturated dicarboxylic acid with 4-12 carbon atoms and 4-12 carbon atoms. It can be produced by condensation of equimolar amounts of 14 diamines. in polyamide Excess diamine is used to obtain an excess of amine end groups over carboxyl end groups. can be used.

Examples of polyamides include borehexamethylene diamine (nylon 66), polyamide xamethylene azelamide (69 nylon), polyhexamethylene sebaamide (69 nylon) 10 nylon), and polyhexamethylene diamine dodecanoamide (612 nylon). polyamide produced by ring-opening of lactam, i.e. polycaprolactam Tam, polylauryllactam, poly-11-aminoundecanoic acid, bis(para-amin) (minocyclohexyl)methandodecanamide. In the present invention, the above By copolymerization of two types in a polymer or terpolymerization of the above polymer or its components Manufactured polyamides: e.g. adipic acid, isophthalic acid hexamethylenediamine Copolymers and the like can also be used. Polyamide is a linear chain with a melting point of 200℃ or higher. The above is preferable. Containing as much as 99% by weight polyamide in the formulation however, the formulation may contain 60-99% by weight, and narrower 80-95% by weight. % polyamide. Due to "semi-crystalline", U.S. patent 4. 410.661, the polyamide has a definite melting point and measurement as described in columns 1 and 2 of It means that it has a possible heat of fusion.

The ionic copolymer contains at least one alpha olefin and at least It is formed from repeating units of one type of alpha, beta unsaturated carboxylic acid; the acid moiety of is at least partially ionized by the metal ion. alpha - The number of carbon atoms in the olefin is preferably 2-6, and the number of carbon atoms in the acid is preferably 3-6. stomach. The alpha olefin is ethylene and the acid is acrylic or methacrylic acid. It is preferable that there be. Other polymerizable comonomers, such as acrylates or meth Acrylates can also be present. The metal ion can be monovalent, divalent or trivalent, e.g. Na.

It can be Zn, AI, K, etc. A typical copolymer contains 70% Lead neutralized ethylene/isobutyl acrylate/methacrylic acid (80/10/10) is included.

The polyethylene used can be high density or low density. functionalized polyester Tyrene is polyethylene containing up to 10% carboxylic acid or anhydride functionality. I can do it. These are described in Epstein U.S. Patent No. 4,174,358. has been done. The weight ratio of polyethylene to functionalized polyethylene is 1:1- 2:1 is preferable.

A small amount of anhydride-rich polymer constitutes the third additive component. This ingredient is styrene Polymers containing alternating chlorine and maleic anhydride (e.g. ARCo Chemical SMA 3000) sold by Al, ethylene and maleic anhydride. Alternating polymers (e.g. Mon5anto Chernica) Comp ethylene-maleic anhydride polymer) or higher olefin produced by any Maleic anhydride polymers (e.g., maleic anhydride polymers manufactured by Gplf Oil Company) tadecene-maleic anhydride polymer). including alternately means that the comonomers serving as units are substantially alternated.

The ingredients used to form the formulations of the present invention can be prepared by tumble blending the ingredients and forming the formulation. It can be combined by feeding it into an extruder of a blow molding device. but It is preferable to uniformly disperse polymers with high anhydride content, using a melt extruder ( equipment such as an axle screen extruder or a twin screw extruder). It has been found preferable to melt blend the ingredients using a method of melt blending the components. The blended product is Cut the extruded strands into pieces), dry them, and use an extrusion blow molding machine. It is used for blow molding purposes to produce hollow products such as containers.

Example The examples shown below are made from adipic acid and hexamethylene diamine as polyamides. 66 polyamide “Zytel” (number average molecular weight 16°000-20, 000). Ionomer polyolefin additive is 70% zinc neutralized. It is a tyrene-methacrylic acid (90/10) copolymer ("5urlyn").

Unmodified polyethylene U such as linear high molecular weight polyethylene manufactured by Phllips Mar]ex HXM 50100 (shown as THDPE in the table below); or Dow “Linear low” density polyethylene manufactured by Chemical Dowlex 204 5. When using LLDPE (indicated as LLDPE in the table below), anhydride-modified polyethylene ( Modified with 1% maleic anhydride (denoted as anhydride-modified PE in the table) was used as a compatibilizer. use

The high anhydride copolymer used was: SMA-3000. ARCOChe Styrene-maleic anhydride copolymer by mical EMA-31, Mon5anto Chemical Co, manufacturing ethylene- Maleic anhydride alternating copolymer FA-18, Gul　f　il　Co, (chemical It is an octadecene-maleic anhydride copolymer produced by the Academic Department).

The number average molecular weight was measured using a Waters 150c gel permeation chromatography device. The measurement was carried out at 110° C. using metacresol as a solvent.

The melt viscosity is the melting capillary manufactured by Kayeness Te5t Instrument. It was measured with a rheometer. Melt flow is F, F, 5loan Corpora Melt index manufactured by tion, Wimington, Delaware It was measured using a standard device.

Materials are processed using a single-screw 5terl extruder or a twin-screw extruder. Extrusion compounding using a Werner & Pf 1eiderer extruder and drying dried and blow molded into one quart containers using a Rocheleau extrusion blow molding machine. Used for mold.

Blow molding method Compound a suitable mixture of materials and use an extruder with a 2 inch screw. Melt extrusion is performed, and the molten polymer is turned into strands and cut into small pellets. Ta.

The pellets are then fed into a blow molding machine with a 1 to 1 part 2 inch diameter screw. It was then molded into bottles with a capacity of 1 quart. The temperature of the extruder is approximately 270℃ I kept it. Cut and blow, stopping the extrusion before forming the container, and removing the melted powder. Pushed vertically by having the lison stand up and support its own weight The strength of the melt tube (parison) was qualitatively evaluated. The strength for which parison is suitable If the temperature is not high enough, the parison will easily break and the melt will blow into the container. It cannot be formed and falls off. Melt tube (parison) if it has suitable strength supports itself without breaking and can be used to form containers by blowing.

Comparative Example 1 80 parts of 66 polyamide with a molecular weight of about 16,000 and 20 parts of an ionomer copolymer. With polymers, the extruded melt does not have enough strength to support itself and rapidly It broke and fell. Containers can be blow molded using formulation 100 of Comparative Example 1. 1 part of styrene and maleic anhydride alternating copolymer (SMA 3000) Both were melt blended. Blow molding as described in Comparative Example 1 results in excellent blow molding. A type container is obtained.

Table 1 shows the components used in Comparative Example 1 and Example 1 and the results of blow moldability.

Examples and comparative examples using the same method and the components shown in Table I and Table II The blow molding results shown in the table were obtained.

L table Copy and translation of corrected sound) Submission (Article 184-8 of the Patent Law) June 29, 1991

Claims (4)

[Claims] 1. fundamentally: a) 99-65 parts of semi-crystalline polya with a number average molecular weight of 10,000-25,000; Mid; b) 1-30 parts per cent by weight based on the polyamide 1) partially or completely gold at least one α-olefin and at least one neutralized with a cation of the genus an ionic copolymer of α,β-unsaturated organic carboxylic acid, or 2) Polyethylene and functional groups containing up to 10% by weight of carboxylic acid or anhydride functional moieties. a mixture of functionalized polyethylene; and c) 0.1-3 parts by weight of male Inic acid anhydride and alpha-olefins such as styrene, ethylene or octadecene and containing at least 15% by weight of anhydride units. A formulation consisting of a polymer. 2. The formulation according to paragraph 1, characterized in that the polyamide is nylon 66. A compound with a characteristic. 3. A formulation according to paragraph 1 or 2, wherein component (b) is partially metallic in the acid moiety. at least one alpha olefin neutralized with cations and at least is an ionic copolymer of alpha, beta unsaturated organic carboxylic acids. A compound characterized by: 4. In the formulation according to paragraph 1 or 2, component (b) comprises polyethylene and up to A blend of functionalized polyethylene containing 10% by weight of carboxylic acid or anhydride functional moieties. A compound characterized in that it is a compound.