TW574267B - Flame retarding phenolic aldehyde resin with long term storage stability - Google Patents

Abstract

This invention relates to a flame retarding phenolic aldehyde resin with long term storage stability, in which the phenolic aldehyde resin is made by reacting resorcinol with furfural and thus can be stored at room temperature for a long time. When polyformaldehyde is used as a hardener, the phenolic aldehyde resin can be applied to protrusion molding and high temperature molding of bulk molding compound (BMC) and sheet molding compound (SMC).

Description

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Various acid resins produced by the reaction, good workability, various FRP molding processes

The present invention relates to a simple resin made from Jane # tp, which is mainly made of resin. The suitable curing agent for furfuric acid 2 can be suitable = made from phenol made with FRP molding processing, whose acid / panmol ratio is greater than that of i-tree. ;; = Benzene reacts with methyl alcohol, resol resin properties at room temperature: Resol resin. However, if the county-level six children are not good, the storage period is usually 1 month, and then refrigeration equipment is required. Because ... S. 1 resin

ΐ ::! ί It is very difficult to popularize the application in tropical or tropical countries, usually: f 卜特 '' demand: order production, can not be produced in advance so that it can be supplied at any time. When the "poor storage" is exported, the transportation vehicle needs to be stored 7 times, which increases the cost, and cannot compete with the local resol resin.: ,,, and solves the storage problem of FRP molding guarding resin, " M 〇1 can be modified by adding ethylene glycol, glycerin, etc. or introducing functional groups, but there is no publicly available and feasible method. Generally speaking, the effect of prolonging storage life is limited. On the other hand, use liquid n 〇v〇lak phenolic resin 'with appropriate hardener, can be used in FRp molding processing, has become an alternative considered by the industry, and has specific examples:

(1) In Japanese Unexamined Patent Publication No. Hei 6-192360, a reaction between phenol and formaldehyde is firstly performed, and then a mixture of isocyanate is added to prepare a liquid η 0 v ο 1 ak resin. This η 〇 v ο 1 a k resin uses polyoxymethylene as a hardener and is used in pultrusion. (2) In Japanese Patent Application Laid-Open No. 8-1 804, novolak resin is prepared by reacting resorcinol with formaldehyde; and then res 〇1 resin is prepared by reacting phenol with formaldehyde and furfural. novolak and resol are mixed at 20/70 for pultrusion

Page 4 574267 | No. 90112331 V. Description of the invention (2)

Novolak resin has storage advantages only. Resorcinol is usually added. However, the above-mentioned (1) tree properties / Brafibita phase, 〇, ΛΑ and "97" are not ideal for hardening at room temperature. (2) Although the resin has proven to be applicable to the FRP molding processing method, the manufacturing process is complicated and must be: a variety of resol resins. In response to the improvement of the above-mentioned defects, the present invention provides a aldehyde resin, which has a simple process and good workability. It can be used with a variety of FRP molding and sclerosing agent greases that are compatible with a wide range of temperatures. Furfuric acid is used as a raw material, and the test catalyst is added in the reverse method. The weight ratio of tree and resorcinol to furfural is 15 ~ 1 (). The mesh structure is insufficient during medium-sized, which affects the mechanical properties. Less than j has a negative impact on hardening properties and gelation time. , '· For storage, m-benzene is solid at room temperature and its reactivity is more reactive than that of benzene. It is mainly used for hardening at room temperature, such as in industrial soils, to shorten the hardening time. It is added to the reaction between furfural and phenols. In addition to the double bonds undergoing additional condensation, it can also be polymerized to form a network structure. Generally, t, containing: ° South%. The resin has excellent fluidity, but the hardening is relatively slow. The alkali catalyst used in Kushiro's phenolic-resin synthesis can be salts such as sodium hydroxide, barium oxide, calcium hydroxide, magnesium hydroxide, etc., and it can be used by mixing two or more kinds of emulsified potassium. After using it earlier, or adding polymethyl methacrylate to the phenolic resin prepared by the present invention, the viscosity still does not increase significantly after several hours. D "Warm mixing ...

Page 5 574267 ~ -i ^ ~ Bi233i_Year Month and Day 倏 π: _ V. Description of the invention (3) '-80% or more, it can be rapidly hardened, which is very suitable for pultrusion. Of course, it can also be made into a ball-shaped molding compound (BMC) or a sheet-shaped molding compound (SMC). I acetic acid is preferably in powder form, and can also be used in conjunction with other horses. When using polyformic acid alone, the dosage ratio of polyacid resin is 4 ~ 1 $%. The above polyphenol-mixed phenolic resin can be rapidly hardened at room temperature by adding an acid catalyst, and the acid catalyst used can be phosphoric acid, benzenesulfonic acid, p-m-benzoic acid or a mixture thereof, or resoli Commercial finished hardener for phenol resin hardening at room temperature. Hereinafter, the present invention will be described in detail with reference to examples. Example 1 (Resin synthesis) 160 parts of a 2.5% solution of sodium hydroxide in methanol and 4,000 parts of resorcinol were placed in a glass reaction tank equipped with a stirrer, a condenser, and an isobaric titration funnel, and the temperature was raised to 80 Above ° C, furfural starts to drip from the isocratic titration funnel. The reaction was exothermic and was refluxing. The 300 parts of furfural was dropped in 1 hour, and then the reaction was continued under reflux for 2 hours. After the reaction was completed, methanol was added to dilute to prepare 1 000 parts of a phenolic resin. The solid content is 65 ~ 66%, and the viscosity is 1 500 c ps (25 ℃). Example 2 The phenolic resin synthesized in Example 1 was mixed with polyacetal powder and an acid catalyst SW 9610B (a hardener for the curing of room temperature resol phenolic resin at room temperature). The gelation time was measured. The results are shown in Table 1.

574267 __Case No. 90112331_ Year, month, and day five. Description of the invention (4) Table 1: Gelation test resin 10 0 ^ 100 parts 100 parts 1 100 parts 100 parts paraformaldehyde 6 parts 10 parts 10 parts 6 parts 6 parts acid catalyst SW9610B 0 parts 0 parts 10 parts 6 parts 4 parts temperature 8 0 ° C 80 ° C 25 ° C, 2 5 ° C 2 5 ° C 1 Gel time 22 minutes 18 minutes 24 minutes 47 minutes 50 minutes

Example 3 The phenolic resin synthesized in Example 1 was placed at room temperature (20 ~ 30 ° C), and the viscosity of the resin was measured at regular intervals. The results are shown in Table 2. Table 2 Viscosity changes and storage stability Storage period 0 days 30 days 90 days 180 days Viscosity (cps) 1500 1700 1900 2300 Example 4 Mix 100 parts of phenolic resin (from Example 1) 100 parts, 6 parts of polyformaldehyde, 6 parts of SW 961 0B, apply the mixed resin to a glass mat with a defoaming roller, and the weight ratio of the resin to the glass fiber is about 60:40. After hardening at room temperature, the hand laminated sample is then placed at 60 ° C. Oven for 3 hours. Measured oxygen index according to ASTMD 2 8 6 3: 50. In summary, the phenolic resin prepared according to the present invention has storage stability at room temperature and can be applied to various FRp molding and processing methods at a wide range of temperatures.

574267 Case No. 90112331, Amendment V. Description of the Invention (5) The molding method has not been disclosed before the application, and it has complied with the provisions of the Patent Law, and has filed an application in accordance with the law. ΙΒϋ 574267 _Case No. 90112331_ Year Month Day Amendment

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Claims (1)

574267 ^ Case No. ―Text, Application A long-term stable and stable flame-resistant resol resin, which uses polyformic acid as a hardener, can be used in pultrusion, high-temperature molding such as pellet molding (SMC) / sheet molding (SMC). 2. According to item 1 of the scope of the patent application, the levy is based on resorcinol and furfural as raw materials. It is produced by ... . The weight ratio of methane to uric acid to furfuric acid is 丨 == the resins described in the above, where πA · b ~ 1 · 0. Page 10