TW199900B - fiber reinforced furan resin composite and method of preparing thereof - Google Patents

Abstract

A method of preparing fiber reinforced furan resin composite comprising the steps of: dipping fibers in liquid furan resin; extruding the fibers through a squeeze orifice to remove residual resin and air; passing the fiber reinforced resin through a heated pultrusion die to harden the fiber reinforced resin composite; in which the visocity and temperature of the liquid furan resin are 500-3000 cps and 15-35鷯 respectively, and three heating areas are provided with 150-180鷯 in the first area, 180-225鷯 in the second area and 170-220鷯 in the third area.

Description

χ9990Ο Λ 6 η 6 Ministry of Economics + Central # quasi-bureau β work elimination cooperation Du Yinyu V. Description of invention () Technical scope The present invention is a method of drawing and shaping the iron-dimensional reinforced resin composite material, especially related to a zong The teaching method of drawing and shaping of dimensional reinforced furo resin composite material. BACKGROUND OF THE INVENTION Bozer * et al. Disclosed in the paper "Fiberglass Reinforced Furan Composites-An Unique, Combination of Properties" published in the 26th Annual Technical Conference, 1971, Reinforced Plastics / Composites Division, The Society of the Plastics Industry, Inc. The modified furan resin and a series of new catalysts, and the glass fiber reinforced composite materials manufactured by using these materials. This resin-catalyst system provides improved processing characteristics. The resulting laminated product has similar physical properties as those using polyester resins but exhibits excellent chemical resistance and resistance to thermal deformation. (Heat Distortion), flame resistance (Flame Resistance) and low smoke emission (Low Smoke Emission). Bozer and Brown in the 27th Annual Technical Conference, 1972, Reinforced Plastics / Composities Division, The Society of the Plastics Industry, In. · The published "High Temperature and Combustion Properties of Furan Composites" paper reports the chemical resistance of glass-filled fiber furan wax composites at high temperatures, especially for anti-combustion. The page binding line paper is used for the standard use of the "Instrument Standard (CNS) < fM standard (210x297mm) Λ 6 Β6 i999〇〇 V. Invention description () (Please read the precautions and fill in This page) Λ sex number. These composite materials are laminates made by Prepreg and Hand Lay-Up methods.

Selley published the "Furfuryl Alcohol Resins with Low Flame-Spread Low Smoke" in the paper of 29th Annual Technical Conference, 1974, Reinforced Plastics / Composites Division, The Society of the Plastics Industry, Inc., which revealed that it was used in furfur trees The new catalyst of nitrile, and thus improve the operation and anti-high temperature properties of Fushu Nanshu pickle, in this paper, the iron-dimensional reinforced Fushu tree composite material is still manufactured by the layer method.

Bozer and Wat son at the 30th Annual Technical Conference, 1975, Reinforced Plastics / Composites

Division, The Society of the Plastics Industry f Inc. published "Furfuryl Alcohol Resin Systems for Hand Lay-Up and Spray-Up Fabrication". The paper reveals that it is used for hand lamination (Hand Lay-Up) or cloth (Spray-Up) operation method to fabricate the furado tree wax and catalytic stab system of the laminated material of glass-fiber / furado tree wax composites.

Szymanski and Kloda at Chemical Engineering

Progress (Vol. 70, No 1, 1974) published "Polyester and the Ministry of Economic Affairs Central Bureau. Bureau ex Gongxiao tv 'cooperation Du Yin ¾

Furfuryl Alcohol Resins For Corrosion Control &quot; The paper introduces the method of making fiber reinforced composite lining by using Polyesters and furosemide resin, which includes the use of spray up yttrium synthetic fiber stitching (Filament Winding ) Spray Winder Technique, Molding and Laminating -4-This paper scale is used in China National Standards (CNS) T4 regulation tft (210x29_ / public) 199300 Department Central quasi-working consumer ft. · Heshe printed 5i. V. Invention () method. Downing was published in the The Chemical Engineer journal, published in April 1978, in the "Glass Fibre Reinf〇rceci Furane Resins" paper, introducing the glass-broken dimensional strengthened furan tree wax composites in corrosion control 〇rr〇si〇n contro1) For the purpose of use, the introduced manufacturing methods include Hand Lay-Up and Fiiament winding. Ο Ma Zhenji, one of the inventors of this case and his collaborators, disclosed in US Patent No. 4'873,128 A method of pultrusion molding of fiber-reinforced phenolic resin composite materials, in which liquid phenolic resin is maintained at a relatively high temperature of 45-65 &lt; &gt; C during impregnation to obtain a unified viscosity. From the aforementioned technical literature It can be seen that the fiber-reinforced, hiccup resin composite lining has very good physical properties, excellent chemical properties and flame resistance at high temperatures. However, no one has tried to produce high The continuous pultrusion method is used to manufacture iron-dimensional reinforced furan wax composite materials. The purpose of the present invention is to first provide pultrusion-strengthened furan wax composite materials. Method of the invention. The present invention provides a method for the pull-forming of a reinforced furan wax composite material, which comprises impregnating the continuous reinforced woven pomelo with liquid furan resin. A squee hole (squee2e 〇riflCe) to remove excess resin and air, and then through the heating of the technology to move the mold (pultrusi〇n die), it is hardened to produce the required shape of the weave (please read the back first Note for Er to fill out this page) Packing-Bookmark _ Line-V. Description of the invention () Strengthened * Fuduwa wax composite material product, in which the nuclear liquid state, Fuhushu wax is maintained at 15-35 ° during the impregnation process C and has a degree of 50-0-3000cps 'and the heated pultrusion chess set contains at least three heating zones, the temperature of the first stage is between l50-1800 ° C' and the temperature of the second stage is between Between 18〇-225.〇: the temperature of the third stage is between 17〇-22.〇, and the temperature of the second stage is higher than the other two. The liquid furan used in the method of the present invention The tree nitrile contains a large amount of catalytic cough &quot; South Eye Prepolymer (furfuryl aic〇h〇l prepolymer), applicable catalysts include p-methanesulfonate 'maleic anhydride and phosphoric acid, of which p-methanesulfonate's catalytic ability is the strongest, the latter two are weaker. The content of p-methanesulfonic acid is a business polymer 0.5% · 2 · 5% by weight, preferably 0.5-1 · 5% by weight. If maleic anhydride and phosphoric acid are used as catalysts, the amount of catalytic engraving must be increased, or more powerful chess tools should be used Temperature. This liquid cough β-nanshu wax has a pot life of up to about 8 hours at a moderate level, and should be as high as ^. It can be hardened and shaped when the high-speed centimeter / minute passes through nuclear heating. Optionally, a post-hardening treatment is used in the pultruded product of the method of the present invention to improve its physical properties. The post-hardening treatment involves heating it under 10-20-22 ° C for 2_1β hours. The shorter the time required, the faster the drawing speed used in pultrusion molding, and the longer the hardening time required afterwards. A detailed description of the liquid furfuran wax that is not used in the method of the present invention, one of the preferred methods of rylene is to first prepare furfuran drunk prepolymer, and then pre-impregnate the prepolymer and Λ 6 η 6 199900 before impregnation. Description of the invention () One amount of catalysis is uniformly mixed. The method includes P-Tol uene Sulfonic Ac id (0.05-2.5 parts by weight, preferably 0.3-1.5 parts by weight). ) The catalyst is added to 100% by weight of furfuryl alcohol monomer (Furfuryl Alcohol Monomer), reacted at 35-7〇 ° C for 4-6 hours, to a degree of about 300-400 CPS, then immediately The reaction mixture was cooled to the impregnation temperature in an ice bath. At this time, the temperature of the reaction mixture was about 500-8000 cps, and then 0.5-1.5 parts by weight was added, preferably 0.5-1.5 parts by weight. Para-methanesulfonic acid is homogeneously mixed in the reaction mixture. Unless otherwise specified, the term Le Cordon in this description is measured with a Brookfield viscometer in accordance with ASTM D2393. Other suitable catalysts include maleinol ( Maleic Anhyd rid) (or cis-butadiene dianhydride) and dish defeat. Among them is the catalytic ability of para-methanesulfonate Strong, the latter two are weaker. That is to say, in the case of adding equal responsibility, the para-methanesulfonate catalytic activity is strong. Therefore, if maleic anhydride or phosphoric acid is used, the time to react the monomer into a prepolymer The growth can be improved by increasing the amount of Malay liver or dish or increasing the temperature. The above-mentioned diffuse concentration method is maintained at 15-35. (} Under, to maintain at 25 ° 0 in Shixi: preferably, at At this temperature, the viscosity of the impregnated furosemide resin is 500_2000 cps, and preferably 800-1500 cps. As is familiar to those skilled in the art, the viscosity of the impregnated wax in the impregnated tree will increase with the time The increase and increase, the change situation can be illustrated by the following example: when the furan resin is 1-5 C by weight of p-methylbenzylsulfonate catalyzed and engraved sulfonium, its degree of lemma is 880 CPS from the beginning, and slowly increases to 2 hours later It is 1400 cps and 2,000 cps after 4 hours; while when furfural is prepared using 1.0% by weight of <p-methansulfonate, the viscosity rises from 62 cps at the beginning to 4 hours π. Ding 3 and 8 hours later, the paper size is used in the middle of the sleepy S home-like standard (〇15) 4 specifications (2 丨 0X297 male dragon) ( Read the notes on the back * and then fill out this page) Order 'line-approved by the central government of the Department of CX and the cooperation between CX industry and Du Du Si. 5. Description of invention () _ cpse From the above example, we can see that the invention contains It has sufficient stability when it is placed in the impregnated grain, that is, it has a "pot life". The iron dimension used in the method of the present invention, including, functional wire, yarn bundle, thread, Vietnam, cloth or ϋ, etc. Various kinds of continuous forms of reinforcement Ewei, the more commonly used materials are broken _ dimension 'broken function dimension, and poly chain amine-) fiber or hybrid fiber (Hybrid) and other inorganic or organic fibers. The machine used for the drawing forming operation is already well-known in the prior art. For an all-in-one drawing tool, see US Patent No. 3 244,784, the content of which is hereby incorporated by reference. The temperature of the pultrusion chess set is generally slightly higher than the temperature of the tree wax due to the short stay time of the tree wax 10 to 20t: 'Including the size and shape of the product, it also reflects the design of the temperature of the spring chess tool, which is a better practice in the present invention. In the example, two symmetrically clamped chess pieces with a length of 82 cm, a width of 1.27 cm, and a height of η9 cm are used, and the temperature has three heating zones with different temperatures along the direction of pultrusion. Among the two heating zones with different temperatures, the temperature of the second stage is the highest, which is between 18 ° -225 ° C, preferably between KMOjuoc; and the temperature of the first stage is close to the temperature Cover the entrance of the chess set, between UH80. Between 〇, preferably between 160-1700 ° C; and the temperature of the third stage is between 170-20 ° C, to leo-U5. ^ Is better. Since the furosemide prepolymer / catalysis of the present invention has a relatively high reactivity and the furanol prepolymer has been polymerized to a higher degree, under the above mold method, about 100 cm / min can be used Pull the speed and replace the finished product. In addition, as the water content of the by-product in furid resin is less, it is more conducive to the pull five. Description of the invention () Hanging molding operation, so the first stage of the imported part of the chess set is calculated to be above 100 ° C, and the responsibility is to rush out Moisture in resin. In addition, the temperature of the third stage is maintained at a temperature lower than that of the second stage, so as to avoid the moisture contained in the pultrusion into the intelligent product evaporating at the exit of the pultrusion chess set and expanding by JL. The pultruded product of the method of the present invention can be selectively post-hardened as needed, so as to increase its physical and mechanical properties. The temperature and time of the post-hardening process are generally inversely proportional. The higher the post-hardening temperature, the shorter the post-hardening time required. After bonding, the hardening temperature is between 100-22. Between 〇, the time is between 2_18 hours. It is preferable to heat for about 6 hours at 〇〇〇〇. The impregnated resin used in the method of the present invention may further contain an inorganic filler (filler), such as talc powder, calcium carbonate and silica, etc., the content is generally It is 1-1M of the weight of the tree wax. The method of the present invention can be further exemplified by the following examples, wherein unless otherwise specified, its components and percentages are based on weight. The Dinglie embodiment is used to exemplify the present invention, not to limit its scope. Example 1 Preparation of gold-immersed furanxela: Ministry of Economic Affairs, quasi-preparation; “j” The preparation of Peking ’s digestion duin impregnating resin is configured by the formula in the following list i, in which component (2) sg and components ( 3) After mixing i〇g evenly, add to component (1), at 50t: react for 30 minutes, and then add the mixture of component (2) 1g and component (3) 2g 'after reaction at 50 ° C for 3 and a half <At this time, the viscosity was 300 cps), and the fan was cooled for 1 hour. Then press the ingredients (2> 9g and the ingredients are mixed -9-9 Ο 3 Λ 6 It 6 Fifth, the description of the invention), add the prepolymer to stir the hook (temperature 25 &lt; c, viscosity 400 · 600 cps) 〇 Impregnated Fur》 Fine Ingredients of Feifei Marinated (g) (1) Furfuryl Alcohol Monomer 1000 (please read the precautions before filling this page) _____ ___ (2) Ρ- 甲15 (Ρ- Toluene Sulfonic Acid, Monohydrate) Binding 30 Ministry of Economic Affairs, Bi Yang Jun, ^ Consumer Cooperative Yin Yu (3) Ji Zui (1) Made in Changchun, Taiwan, No. CF · 7452, its solid content 80 *, Ledo (25 ° C) 30-70 cps, specific gravity (251〇) 1.15-1.17〇 (2) Test grade, manufactured by Nippon Pure Chemical Industries, Ltd., molecular weight 190.21, melting point 104-107 ^: (3) Test drug Grade, entrusted by the Tobacco and Liquor Sales Bureau of Taiwan Province to entrust the Industrial Research Institute of Chemical Engineering, G alcohol accounts for more than 5% by volume. Ruler-¾ paper.11 · Used in β country-like 1MCNS) ΤΜ regulation tM21fb &lt; 297 public goods) -10-1999G0 Λ 6 It 6 V. Description of invention ( PPG C0. The 764-NT-218 broken woven I6 bundle impregnation encounter, the specific gravity of the core is 2.54, the diameter of a single fiber, the tensile strength of 1621.5 Mpa, or if a hole (or if ice) to remove The excess resin and air are re-introduced into a chess hole with a length of 82 cm, a width of I · 27 cm, and a height of 0.219 cm. Two pieces of symmetrically clamped electric heating chess pieces are controlled by three-stage heating. The first stage and the The length of the third heating zone is IS cm, and the length of the second heating zone is 40 cm. Test for pulling into a hulk product: The above method is pultrusion into a swish product, and its money content is about 57.5 bottles. In addition, its flexural strength (FleXural)

Strength) and Flexural Modulus, as shown in Table 2 below. The flexural test is carried out according to ASTM D79〇. (Please read the notes to the back and fill in this page first) Packing · Ordering-Line · Printed by the Cooperative Society of the Light Industry Consumers of the Central Bureau of the Ministry of Economic Affairs

X99900 V. Description of the invention () ^ ~ Disturbance, strength and disturbing at different pulling speeds; speed cm / min three-stage chess temperature ^^ 丨 &quot; &quot; &quot; &quot; —-Λ 40 70 100 130 150 a ) 636 692 — '丨 丨 481 * &quot;-282 1--1 _ 197 165,215,210 b) 52.3 52.4 49.2 44.5 40.3 a) 554 442 333 170,200,195 b) 39. 6 38.1 35.1--** a) 305 258 137 175,190,185 b) 39.0 36.5 25.6 — — (Please read the precautions before filling in the wooden page) Λ_ _ (a) Disturbance strength: unit: MPa (b) Disruption chess number: unit: GPa Ministry of Economics Shiyang Bureau κχ 工 消 tv's cooperation with Du Yin 3i after hardening treatment: take Qiwen 165-215-210. ○ The above-mentioned drawing masking plastic product (with a content of about 57.5% by volume) of drawing speed 130 &lt;: 111/1 ^: 1 was subjected to curing treatment under the conditions shown in Table 3 below. The flexural strength of the obtained post-hardened products is also listed in Table 3. .12-This paper scale uses 9 (; υ V. Λ 6 Β6 of the Chinese HHS-T4 (210x297 g) L) Chinese version of the paper. Description of invention () Disturbing strength and distorting strength between tables ^ --- Hardening time (hr) 0 6 12 18 24 loo a) 662 728 739 756 769 b) 282 904 968 1045 1080 150 a) 662 772 797 807 824 b) 282 1016 1071 1073 lll8 200 a) 662 898 960 906 837. B) 282--^ 1198 1185 1180 1165 (please read the precautions before filling in this page) Λ Ministry of Economics Biyang and CX Gongxiao $: Cooperative Duin 1i a) Tensile strength: unit Mpa b) Flexural strength: unit MPa As can be seen from the number ηρ in Table 3 below, it is preferable that the subsequent hardening treatment is performed at 200 ° C for 6 hours. The data of this team-Table 3 also shows that the post-hardening treatment can effectively improve the mechanical properties (ie, tensile strength and flexural strength) of the molded product of the present invention. 13-k paper-scale edge-use "黩 家« ^ (CNS) A 4 gauge 怙 （210) ¾ ^^ 199900

V. Description of the invention () Ge Example 2 According to the steps of Example 1, "furan nitrile" was prepared. The wax was placed in the impregnated lees and maintained at room temperature of 25 ° C, then 22, 24, 25 and 27 bundles of HTA-12〇00 broken woven Vera produced by ΤΟΗΟ company through the impregnation tank (the fiber specific gravity is I.77, the single fiber straight is 7am, and the degree of disturbance after pulling is 287.0.4 MPa). Fiber guide hole, true introduction of chess tools, the three-stage temperature of chess tools is I65 t :, 215. (:, 210Ί0, drawing speed is 70 cm / min. Products with different broken fiber content produced according to the above method, using the method of ASTM D790 Conduct the flexural test and perform the tensile test in accordance with ASTM D3039. The results are shown in Table 4 below. 貅 4 Tensile strength and resistance of different broken fiber content (please read the notes on the back to fill this page ) The Ministry of Economics's central purlin: printed by the ΓΑ Industrial Consumers ’Cooperative Society ＄ Dimensional Ruler Zhang Weiwei Content Product” Strength 45.74 49.5 51 _ 5 56.1 Tensile Strength (MPa) 869 948 1070 1360 Flexural Strength (MPa) 400 560 671 790 (CN φ home VI / male 97 2

α- X… Λ 6 Ά'ί__Π6_ V. Description of the invention () Example 3 Add 50g and 100g of talc powder to the impregnated resin prepared according to the steps of Example 1, respectively, as the filler (the talc The powder is made by Hewan Changxing Chemical Co., Ltd., with specific gravity m, average particle size 2.i2u &quot;. After stirring, pour it into the impregnation tank and maintain it at 25 ° C. Use 764 · NT-21β glass fiber produced by PPG Company 15 The impregnation bath meets the impregnation tank, and then enters the chess tool after encountering the fiber guide hole. The three-stage temperature of the chess tool is 165 ° C, 215 ° C, and 210 ° (〇, the pulling speed is 100 cm / min. Dare to contain different The tensile strength of talc powder was tested by ASTM D790 method, and the tensile test was performed by ASTM D3039 method. The results are compared with the products without talc powder. The results are listed in Table 5. In. A s I Ben: r, the same as talc powder content of anti-tensile Tang Tang and Qian Zheqiang complex

(Please read the notes on the back for the first time Jiang Jiang Ϊ? This S equipment-line _ Ministry of Economics + Central Government and κχ 工 消 «-Cooperation Du Yin 52. stone powder content (g) strength 0 50 100 tensile strength ( MPa) 741 758 588 Flexural strength (MPa) 480 525 364 -15-

The size of this paper is based on the China B Jia Zhun (CNS) T4 regulations (2 father 297 male dragon) / 11 1999G0 5. Description of the invention () From Table 5 it can be shown that the responsibility for adding talc powder increases to At 100, it decreases according to the degree, because the ambiguity of the wax is reduced by the addition of the filling, and the catalytic effect of the acid catalytic punishment is reduced. Therefore, in the production of high-filled Shiwei strengthened furfur When the tree wax is molded into a composite material, it can improve the content of the nail stupefying ** or be purified ^ to produce a high-filler and f-shaped composite material. (Please read the back-to-back notes on the general matters first and then the "wooden pages"). Installed, 13T-line · Ministry of Economic Affairs Standard Standard β β Consumer Cooperative Printed 54 镑 度 Ruler Sheet Paper g Pregnancy f

Claims (1)

A: B: CI); Section f), YJJ i v-'· &quot; ·· i 丄 9⑽M%, Sixth, Chinese please if Lifan a: (Amended in September 2011) 1. A kind of weave "Strengthening" the manufacturing method of pultrusion of Fuwa tree wax composite material, including impregnating the continuous reinforcing woven pomelo in liquid, liquid furan resin, and removing the excess through a squeeze 〇rifice The wax and air are then hardened by a heated pultrusicm die to produce a fiber-reinforced furan wax composite product of the desired shape, wherein the liquid furan resin is maintained during the impregnation process At 15.35 ° CitJL has-reduced to 5GG.3 just. Ps, and the heated pultrusion chess set contains at least three heating zones, the temperature of the first stage is between i5〇-: U (rc, the second stage The temperature is between is〇uyc and the temperature of the third section is between 170-220 ..., and the temperature of the second section is higher than the other two sections by about 5-50 ... (please first hear the "back": ^ I will write the notice again-^ 玎 i. 2. Economy.- '. 中 夬 會 會 會 局 民工 消 # Cooperation-printing such as applying for a patent application Method, in which the material resin contains a "flavor" compound and a catalyst, the pure (iv) is 0.05.2.5% by weight of the prepolymer. The compound has a 500-800 cps when it is carried out. 3. The method as described in item 2 of the patent application park, wherein the preparation of the alcohol prepolymer is based on ⑽ parts by weight & two shots alone. 〇525 parts by weight of catalytic riding 35.7. (^ Reaction-between the moment and the degree of the reaction mixture up to 300-400 cps. 4. The method as described in the application specific item, in which the catalysis · 17, fight ·-&quot; S1. 4. 5,000 ⑻ It is selected from the group consisting of p-out Ο-methanesulfonate, cis-butadiene, and phosphazene by Ρ- 出. The method described in item 3 of the patent application circle, where the catalysis is The selected flavor of the family consisting of metzepine, cis-butadiene, and phosphoric acid is as described in item 1 of the patent application, in which the woven-strengthened southern resin composite material is produced After-post hardening treatment. ^ The method described in Item 6 of the Chinese Patent Application, wherein the post-hardening point is 10. - twenty two. . The composite material product is heated at a temperature of 2 · 18 hours ^ If the special method is based on the frequency method, the material for reducing the size of the material is sloping glass fiber, carbon woven fabric, Zhonggu spit one _ heart _, texture, mixed Fiber 4 'or other inorganic or rich weave. f ^ First read the back of Qi; ± Important matters and then write Table 1; • K. • Order ·-, M #; 屮 &quot; Standard '&quot; ΚΪΓIndustry and consumer cooperation R seal &quot; 9. If applying for a patent model The method described in item 1 of the park, the pultrusion of the furan resin composite feedstock can be higher. The fiber is reinforced to 150 Cm / min. 〇10. As described in the method of patent application item 1, Gan Further-contains ~ _ filler. Ride the resin 18 Si. 4. 5,000 (H) .1. 99900 Λ! Β; C: [): 11. The method as described in item 10 of the patent application park, wherein the inorganic filler is the weight of the resin 1-15%, the inorganic filler is talc, calcium, silica or the like. Qi Xian first read the back of the :: ± sound; then write down the page of the matter. Order.-^-. Chinese standard-¾ work consumer t He 19 81. 4. 5.000 (H)