TWI227189B - Pultrusion shaping method of fiber-reinforced phenolic resin - Google Patents

Abstract

This invention relates to a pultrusion shaping method of fiber-reinforced phenolic resin of high strength, flame resistant, low smoke, low chemical smog, including processes of dipping a reinforced fiber in a resin, and harden-shaping by introducing the dipped fiber through a pultrusion mould to be hardened and shaped. The drench basically consists of three kinds of drench: (A) phenolic resol resin; (B) mixture of resorcinol and ethylene glycol; (C) mixture of Hexamine and water; ratio: B/A 1 to 20% weight percentage, C/A 1 to 20% weight percentage.

Description

5 'Description of the invention (1) The present invention relates to a high-strength, refractory phenolic resin pultrusion molding method, a fiber, a strong impregnation solution for the fiber, and a pain-resistant impregnation solution. The solution is very helpful for the stable quality of the preparation. For the mechanical equipment or mold of the molded product, it is a rotten name. , 31 or test catalysts' will not cause the mechanical fiber molding system to impregnate the reinforcing fibers in the pultrusion, so that the product can be continuously labor-saving through the addition of design, and the appearance and properties of the product: 巧 相 田 优 # has become In order to obtain the best pultrusion in the method of processing hardened materials # σ „.. m seat Wan ° °, 1 ^: (a) ^ t ^ ί τ t is reactive, and the resin has good fiber Impregnation effect. Commonly used fats include unsaturated polyesters, epoxy resins, and phenolic resins. Fats and fats have excellent flame retardance, low smoke, and low toxic mist characteristics. Relative ::; 'But it cannot be denied that in practical = there are still many problems to be overcome. # In development, in order to meet the above four characteristics, the phenolic impregnation methods in impregnation tanks can basically be divided into three categories: ^ (1) Addition to Fan Road Resin Acid catalysts, generally speaking, are acid-tactile, so they can be called two-liquid type. For example, the Republic of China Patent Publication No. " Catalysts. ◦ State 7 2 (2) Alkali catalysts are added to the resins. For example, in Japanese Patent Application Laid-Open No. WH05142, hydrogen is used. Plutonium oxide is used as a catalyst. Calcium oxide is used as a catalyst. (3) A special reactant is added to the rattan resin, and the special reactant may be solid.% 'For example, in Japanese Patent Application Laid-Open No. 6-192 2 3 60, polymethyl methacrylate is used; The special reactants may also be liquid. For example, in Japanese Patent Application Laid-Open No. 8-1804, a resin containing bran resin res ο 1 is mixed with m-benzene dipentoxide n 0v ◦ 1 a & resin, which is a two-liquid type. However, for molding machines that must be operated at South temperature, the use of acid catalysts or alkali catalysts will cause corrosion problems and affect service life. How can solid catalysts or special reactants be dispersed quickly and uniformly? It is not easy to solve the impregnated resin to ensure the uniform quality of the product. Therefore, the two-liquid type without acid and catalyst seems to be the best choice. However, as mentioned above, the resol resin containing furfural And novovlak resin containing resorcinol must be specially made The cost is very expensive, which affects the willingness of pultrusion manufacturers. The purpose of the present invention is to provide a pultrusion method to solve the above-mentioned shortcomings. Among them, the impregnating solution is mainly a mixture of three solutions, namely (A) phenolic K $ 〇 丄 resin, (B) a mixed solution of resorcinol and ethylene glycol, (c) a mixed solution of hexamethylenetetramine and water. (A) novolac res〇1 resin does not need to be specially produced ' Appropriate commercial phenolic resin products can be used, but the viscosity is between 1500 and 8000 cps, and preferably between 3,000 and 6,000 cps. Resorcinol is a solid at room temperature and its reactivity is higher than that of phenol. It is used for applications such as adhesives for curing at room temperature, or it can be added to grease to shorten the curing time. In the present invention, the resorcinol and ethyl alcohol mixed liquid (B) to (A) is used in the proportion of 丨 ~ "wt%, less than one

Page 6 1227189 j No. 90110076 _Year month and month Amendment V. Description of the invention (3) Incomplete hardening, more than 20% may affect mechanical properties, and priority is 2 to 10% The effect imparted to formaldehyde and ammonia has long been widely used as a hardener for phenolic resins, but it is a white or colorless solid at room temperature. In the present invention, the use ratio of the mixed solution of the hexamethylenetetramine and water (c) to (A) is 20% by weight. If less than 1%, the hardening is incomplete, and more than 20% may affect mechanical properties. Priority is 2-8%. Additives such as release agents and surfactants or fillers may be added to the impregnating solution as needed. Reinforcing fibers include continuous forms such as silk, yarn bundles, ropes, cloth, or felt, and the materials include glass fibers, carbon fibers, polyamide fibers, or their blended fibers. Among them, the glass fiber used by Yan Jun resin is not completely the same as that used by ordinary unsaturated polyesters, and it is suitable to be about 1000 g about 丨 00 ～ 4 ～ 00 g. 'Too detailed, there are handling difficulties when increasing the number of fibers. The design of the mold is very important for high-speed pultrusion. The length of the mold is preferably 50 to 100 cm. When the length is less than 50 CD1, the retention time is insufficient to sufficiently harden the molded product. Generally, the temperature at the entrance of the mold is 14 ~ 15 °, and the exit is 170 ~ 190 ° C. According to industry experience, if the maximum temperature of the mold is lower than 1 5 5 C ′, the molded product cannot obtain sufficient mechanical properties. Therefore, the mold used in the present invention has a multi-stage rising mold temperature. At least one of the heating belts has a temperature higher than 160 ° C, and preferably 170 to 190. (:. ^ In order to enable the panel reviewer to further understand and understand the purpose, technical features and effects of the present invention, the technical content is described in detail as follows: 实施 例 1 (Mixed resorcinol and ethylene glycol Preparation of liquid (β))

1227189 Case No. 90110076 Revised 5th year, description of the invention (4) Mix, heat slightly to 3 5 ~, and heat up 1: 1 m-phenylene and ethene 4 5 ° C, search and mix until completely dissolved, Filter it. Example 2 (Preparation of hexamethylenetetramine and water mixed solution (c)) A hexamethylenetetramine with a weight ratio of 6: 7 was mixed with water, slightly heated to 3 5 to 4 5 ° C, and stirred After it is completely dissolved, it is filtered. … Example 3 100 parts of the phenolic resol resin (A) were mixed with 6 parts of (B) (obtained from Example 1) and 3 parts of (c) (obtained from Example 2) using ⑽9630 'from Shangwei Company, In addition, 0.5 parts of a surfactant (Shang Wei Enterprise sw 1201) and 1 part of a release agent (Axel INT 1185) were added to prepare an immersion solution. The continuous glass fiber bundle was passed through an impregnation tank containing the impregnating solution by a Lago machine, and then pultruded through a heated mold. The mold was preset to be 180 ° and 185 C two-stage heating, and the drawing speed was per minute. 35 cm. Comparative Example 1 Phenolic aldehyde in Example 3! Resin (A) was changed to Changchun Petrochemical PF 750, other conditions were the same. The molded articles in Example 3 and Comparative Example 1 were subjected to post-hardening treatment at 120 ° C for 3 hours, and then tested for mechanical properties. The results are shown in Table 1:

1227189 _ Case No. 9011076_ Year Month Date _ Amendment V. Description of the invention (5) Table 1 Mechanical properties of pultrusion products Unit test method for mechanical properties Example 3 Comparative example 1 Tensile strength MPa 345 296 ASTM D638 Tensile modulus MPa 2620 2330 ASTM D638 flexural strength MPa 270 296 ASTM D790 flexural modulus MPa 32300 19400 ASTM D790 Barcol hardness — 50 50 ASTM D2583 According to the results in Table 1, the present invention can be applied to different reso 1 resins, which Mechanical properties meet general engineering requirements. Furthermore, the molded product of Example 3 was tested for flame resistance, poisonous smoke, and the like. The results are shown in Tables 2 and 3. Table 2 Flame resistance test of pultruded products; Resin type Flame diffusivity Smoke density Oxygen index ASTM E162 ASTM E662 ASTM D2863 Unsaturated Polyester Resin > 75 > 400 20-30 Only Unsaturated Poly S-tree 18-24 140-220 30-50 Grease. SW 963Q (Example 3) 1.8 4 55. 5

Date

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According to the record, the pultrusion produced according to the present invention exhibits characteristics such as flame resistance, low smoke, and low toxic fog. The characteristics are superior to composite materials composed of other resins, thin 2 smoke, low 4 building, and public. Related fields such as transportation. The "impregnation" function is used in 4 pultrusion methods of the impregnating solution have not been disclosed ☆ mouth 2 = preparation method and the requirements of {, apply according to law. Month and month] Paid together 3

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Claims (1)

122718¾ VI. Patent application for bacteria tt ^ 90〇〇〇76 means to modify the pultrusion molding method of fiber reinforced phenolic resin moldings containing continuous ^ ground Jiang species, colonization =: set several reinforcing fibers to draw the phenolic resin , Hardening agent, impregnating solution of horse ^ and other additives, and then the impregnated fiber is pultruded through = a force ^ hot mold 'to make the fiber-reinforced phenolic composite product of the desired shape by curing and molding, which is characterized by The impregnating solution is basically composed of three solutions: (A) a phenol resol resin, (B) a mixed solution of resorcinol and ethylene glycol, and (C) a mixed solution of hexamethylenetetramine and water. The ratio (b) / (a) is 1 to 20% by weight, and the ratio (C) / (A) is 1 to 20% by weight. 2 'The method according to item 1 of the scope of the patent application, wherein the fiber comprises a continuous form of reinforcing fiber such as silk, yarn bundle, rope, cloth or felt. 3. The method according to item 2 of the scope of patent application, wherein the fiber material includes glass fiber, carbon fiber, polyamide fiber, or a mixed fiber thereof. Page 12