TW446721B - Elastic thermosetting complex compound of epoxy resin and polyurethane and the manufacture method - Google Patents

Abstract

This invention provides an elastic thermosetting compound resin of epoxy resin and polyurethane. The compound is characterized by using different ratios of bisphenol-A and chloropropylene oxide to form bisphenol-A/chloropropylene oxide compound through polymerization and by the formation of the secondary hydroxyl structure. In which the hydroxyl number is 0.1-20. Such compound can provide the reactive activity for mixing, modification and grafting. Isocyanate (NCO) containing aromatic or aliphatic compositions of 1-3 isocyanate functional groups and polyol or amine materials are polymerized with the addition of 0-4% of activation agent of tertiary amine or metals to form oligomers with residual isocyanate groups. Another catalytic component has a NCO% content is 0.1-24% based on the oligomer and viscosity ranging from 1000-100000 cps. Through addition polymerization of the active secondary hydroxyl groups of the isocyanate residual compositions and the bisphenol-A/chloropropylene oxide complex compound or blending the products at the presence of the tertiary amine or metal catalytic agent and at 20-110 DEG C, yellowish transparent viscous polymer can be formed. This polymer can be cured by curing agent of epoxy resin containing polyamide, polyamine, anhydride, and Lewis salt base to produce hard, tough or flexible elastic adhensive thermosetting compounds with high molecular weight made of elastic thermosetting polymer of epoxy resin and polyurethane.

Description

446721 V. Description of the invention (/ The present invention can make the extremely useful building materials in the market such as stone, magnetic 4 ', wood, metal stainless steel, etc. sticky, flexible, acid rain-resistant composites and manufacturing methods. There are various proposals for the adhesive bonding method, for example: applying cement tiles with seaweed powder mixed with cement. After cement hydration, due to strong rigidity and large shrinkage, it is easy to cause poor functions such as porosity, water seepage, leakage, and tile shedding. Moreover, the durability is poor, and it is easy to be neutralized by acid rain. The white carbonate compounds appear on the wall, which is commonly known as the white bloom phenomenon, which causes the appearance of spot defects. In Taiwan, which is subject to many earthquakes, the cement adhesive is not elastic and resistant to It can withstand earthquakes and cannot withstand the shaking of high-rise buildings, and it is possible that the tiles loosen and hurt people. The elastic thermosetting composite formed by the epoxy resin and polyurethane of the present invention is mixed and hardened before hardening. Adhesive, effective bonding of all kinds of building materials, and waterproof, shockproof, and acid rain resistant. In addition, in the past, the acid-resistant tile floor has been made of pure epoxy resin hardened material as an adhesive In some cases, although the epoxy resin has strong adhesive effect and good acid resistance, its hardening speed is too fast, the hardened product is too rigid, and it cannot withstand the contraction and expansion of the cement structure building due to temperature difference, resulting in tension. Defects such as cracks, seepage, leakage, etc. The epoxy resin of the present invention has elasticity, large flexibility of lying body, strong adhesion and long operable time, and can be easily applied to adjust the gap between the gap and the side seam, resulting in the quality of ifj Magnetic monument interface. Also, the epoxy resin has poor binding to metal stainless steel, is easy to form peeling off, and has poor resistance to metal bending, so it is not suitable. The present invention provides rich t paper scales and is suitable for use in China. Standard (CNS) A4 specification (210 X 297 mm)-= ---------- t -------- order --------- line (please read first Note on the back, please fill out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 446 72 1 Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _____B7_ " '----- V. Invention Description (i) The dynamic and flexible characteristics are most suitable for the joining of metal materials with tough and flexible characteristics. The buildings, office buildings, factory buildings, warehouses, etc. that are built, are usually designed with steel structures directly connected to the stairs. Traditionally, the steps are painted with paint. Because they are not wear-resistant, they need to be brushed and maintained frequently, which affects the use of construction facilities. If it is changed to cement mortar coating and then attached with magnetic tiles, in addition to increasing the weight of the building, this construction method is not resistant to impact and peeling and cracking, and can be obtained by hardening the elastic thermosetting resin and hardener of the present invention. The integrated adhesive floor tile has completed the present invention. Therefore, the present invention provides: The present invention relates to a hardened composite of a thermosetting elastic resin composition, which is characterized by using an epoxy resin and a polymer containing a second warp, The isocyanate group-containing polyurethane prepolymer is mixed with resin and grafted to form a resin body, and then the amine series functional group hardener is integrated at room temperature or high temperature to complete the salting. Another object of the present invention is to provide a method for manufacturing the above-mentioned resin composite, which is characterized in that the second hydroxy-containing epoxy resin composition is pre-polymerized with any isocyanate-containing polyamino ester, in In the presence of an activator or catalyst, the reaction and kneading bond together. Then, the reactant is tightly hardened with another unhardened amine functional group. The detailed description of the present invention is as follows: (a) The molecule of the hydroxyl-containing epoxy resin structure contains at least 1 to 15 functional groups of a second hydroxyl group, a hydroxyl group, and an epoxy functional group composition. (b) Hydroxyl-containing epoxy resins can be formed by polymerization of bisphenol and epoxy propane, or NOVOLAC phenolic modification, 'bromide modification, hydrogenation modification, or BPF methyl p-diphenol modification. ____ _ This paper size applies to China National Standard (CNS) A4 (210 X ^ 97) -I Pack! ί Order ----- I --- line (please read the precautions on the back before filling in this page) 446721 A7 B7 V. Description of the invention (Even) Its (a) ingredients contain warp-based epoxy resin at room temperature Its viscosity is 100 cps to 100 000 cps, and it is preferable that 'R is hydrogen or methyl' n is 1-15 as shown by the following general formula (1). Λ CH2—CH-CH2-

CH2 a CH-CH2 ~

0-CH2-CH-CH2 and the formula (1) R is a substituted or irreplaceable alkyl group, preferably an alkyl group having 1-4 carbon atoms, and may be methyl, ethyl, propyl, etc. Saturated alkyl or hydrogen (C) is an isocyanate-containing polyurethane, a prepolymer that reacts with a diisocyanate and a polyol, and is a liquid or paste-like organic compound at room temperature. The substance 'has a viscosity of l (X) 0cps to 100,000cps, and the following general formula (2) is better: R-0-CNR' (2) Specifically, as in (b) IT- NCO organic isocyanate is as follows ρ (1) (Please read the precautions on the back before filling in this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

NCO NCO

CHj OCN ^^ MCO Benzene diisocyanate 4.4 Methylene diisocyanate OCN-CHi-CHi-CHi-CHz-CHi-CHs-NCO Hexamethylene diisocyanate ® National Standard (CNS) A4 Regulation " ^ 2 ^ & 7 · 446 721 A7 B7 V. Description of the Invention (Minutes) Isophorone diisocyanate CH3 > i ^ NC0 C 出 ζΓ CH3 CH2-NC0

4.4 Methylene dicyclohexyl diisocyanate In R'NCO, there are from 1 to 3 isocyanates, preferably 2 'which may be aliphatic or aromatic compounds. Among them, R-OH is a polyol part, a fluid or solid compound containing a hydroxyl functional group or a leg functional group, the number of functional groups is from 1-8, preferably 2-3. Such as

W Η0- RCO 'II 0 -0 ΗPolymer_bisolΗ0 _ £ CH: _CH = CH-CH23-〇H Polybutadienyl diol H0- CH2-OH-I CH3 Polypropylene diol III I- -------- I 1--Order ----- --- Line- (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

ΗΟ ~ · ^ ΟΗ2〇Η2〇Η2〇Η2〇 ^ -OH polybutenyl diol in the isocyanate residue-containing prepolymer obtained by the polymerization reaction in the formula (2) the weight percentage of isocyanate groups remaining 0.1-24% of fluid, response b The size of the private paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 446721 A7 B7 V. Description of the invention (Wide) The temperature is from 20. C-110. C. The reaction process can be adjusted with an activator or catalyst to make the reaction fast or complete. Activator, catalyst containing tertiary amine or metal catalyst, base structure, such as dibutyltin dilaurate, octyltin salt, magnesium, cobalt, lead'bismuth, zinc and other organic metal salts, DABC0 catalyst Or its compound combination 0 (1) The product of formula (1) and the product of formula (2) are grafted and infiltrated by mixing, infiltration, reaction, etc. to achieve the effect of improving the quality of the rack. The mixing ratio is composed of the components of formula (1) The 2PHR-200PHR, based on the hydroxyl official equivalent of i20% -2%, is crosslinked to form an elastic thermosetting composite material of epoxy resin and polyurethane. The reaction temperature can be from 20 ° C to 110 ° C. The reaction process can be adjusted with (c) series of activators or catalysts to complete the reaction and homogenize the polyurethane bonds. The schematic reaction formula is as follows:

0H

〇CN Poly-leg formic acid_Polypeptide — If — — — — —! ^ Illllli ^ 1! (Please read the precautions on the back before filling out this page) OH Hydroxy Epoxy Resin Intellectual Property Bureau Staff Consumer Cooperatives Printed T〇lcl; = 0 < 3 activator (C) Η -0 Ν—clo 丄) / 3 yi \ 7 / This paper size is applicable to China National Standard (CNS) A4 (210 X 297 ^ i " j "672 1 A7 --- ^ __________ B7__ 5. Explanation of the invention (4) (3) The product of formula (4) has most of the epoxy groups remaining, some of the hydroxy groups or very few of the isocyanate groups, providing the required application fields. Cross-linking, bonding and other characteristics and drying speed. Among them, epoxy and amine groups are cross-linked to form a polymer complex, and the second hydroxyl group and the original residual (3) type component hydroxyl group provide strong bonding characteristics to different materials. The amino phosphonate bond in the joint is stable in the formation of impact resistance, shock resistance, and shock absorption, so that the polymer has the functions of toughness and flexion. (3) The hydrazone molecular product of the formula is crosslinked with an amine system. In order to adjust its fluidity and improve the mechanical strength of the molded product, it can be combined with a flow modifier. The filler uses a modified flow agent of formula (3) to octyl phthalate, butyl phthalate, triisooctyl phosphate, epoxy soybean oil, process oil, paraffin, etc. from 0.5- 30% is added. (3) The reinforcing filler of the formula is Shen; Dian Xing; g Xi Shi forged; G Xi Shi, fired Shi Xi Shi 'forged titanium oxide and other reinforcing fillers. Among them heavy carbonic acid | Bow, crushed quartz, diatomaceous earth, asbestos, talc, iron oxide, zinc oxide, etc. are non-reinforcing, and can also be added. In order to obtain moderate operability, hexamethylsiloxane, Trimethyl Ministry of Economic Affairs can also be used The Intellectual Property Bureau employee consumer cooperative prints the organic silicides of chlorosilane and polymethylsiloxane as fillers for surface treatment and then uses them. (3) The composite material can also be used with other pigments, flame retardants, and heat resistance. Additives and plasticizers provide additional temperature resistance. The elastic thermosetting compound formed by the epoxy resin and polyurethane of the present invention

446721 Printed by A7 B7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs 5. Description of the invention (/) The composite system hardens and reacts with the hardener under normal temperature or heating conditions, or it is an adhesive composition whose forming operation and bonding process are sensitive to temperature The viscosity is high, the temperature is low, and the cross-linking reaction is fast; otherwise, the viscosity is high and the cross-linking is slow. The schematic diagram of the simulation test device for the adhesive drawing sample used in the examples and comparative examples is shown in Fig. 1. Brief description of the figure: Sketch of the simulation test device for the adhesion drawing of the sample. L frame 5. Auxiliary frame 2. Bottom material. 6. Wall monument 3. Installation of iron parts 7. Test adhesive 4. Steel sheet [赏 施Example] The following examples and comparative examples can specifically illustrate the present invention, but the present invention is not limited to the following examples. In addition, the "part" shown in the following examples means weight = and the viscosity means 25 at room temperature. (: Value at the time.) To 100 parts of methyl isocyanate diisocyanate monomer, add 570. parts of polypropylene glycol with a molecular weight of 2000, and add 0.5 parts of activator at a temperature of 80 ° C. The activator is dibutyltin dilaurate, and the reaction addition is continued at a temperature of 80 ° C. The reaction time is 5 hours to obtain a mixture A with a viscosity of 100 poise and an isocyanate residue content of 3.5%. 'Also in the reaction furnace Put 10◦ parts of the bisphenol-A and epoxy propane heavy compound into it, the molecular weight is 380, viscosity is 100 poise, and the temperature is raised to 80. c reaction to this paper scale is applicable to China National Standard (CNS) A4 specification ( 210 X 297 mm) --- J ---- I ----- -------- Order -------- Slow (Please read the notes on the back before filling this page ) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 6 7 2 1 A7 ___B7___ V. The invention said that the end point of the sun and moon (p) dimension point was determined to be synthesized with an isocyanate residue below 0.2%. The holding time is For 10 hours, a slightly yellow transparent mixture B with a viscosity of 500 poise was obtained. The molecular end of the mixture B ′ was an epoxy group, and the amount was 100 parts. = 30 parts of dry silica with a specific surface area of 2,000 m / g, adding 30 parts of treated carbon, 2 parts of black carbon, and 18 parts of calcined magnesium silicate. After mixing at room temperature by mixing and rolling, add 20 parts of functional polypolyamine compound. The above mixture is often stirred and mixed at a warm temperature, and a sheet test specimen with a thickness of 2 · is coated with a trowel, and the adhesive hardening reaction of the tile is performed. The test specimen is shown in Fig. 1 and tested. 7 days of health can obtain a tensile strength of 40kg / cmZ, an elongation of 50%, and an elastic bonding effect of 20kg / cm2 when pulled out. In addition to strong adhesion, it also has pressure resistance and impact resistance. Impact resistance is 2kg / m high It is not damaged, and the adhesive can be operated for 3 hours. [Comparative Example 1] Add 2 parts of seaweed powder to 100 parts of water. Stir for 30 minutes, and add 2 parts of cement components before stirring. Stir to form a paste-like water solution for use. 1 part of water solution containing seaweed powder, slowly add 180 parts of cement powder to the stirring, and stir thoroughly Evenly to thick paste, then coated into 2cm thick test piece and tile adhesive hardened test body, test And the test piece was re-tested after 28 days of health, and it was found that the test piece was slightly bent and broken, no tensile strength, no elongation performance, and its adhesive pull strength was only 2.5 kg / cm2. The tile and the cement block were peeled off.! ° This paper size applies China National Standard < CNS) A4 Specification (210 X 297 mm) ------------ X -------- Order --------- Line I ( Please read the precautions on the back before writing this page) 446721 A7 V. Description of the invention ([Comparative Example 2] ^ 100 parts of molecular chain ends are cyclofluorenyl, molecular weight is 38Q, liquid type bifen-A epoxy The chloropropane superposition body has a degree of 100 poise, and 50 parts of the amine compound containing diguanyl group is added, and the mixture is stirred at room temperature for 2 minutes, and then a 2_ test piece and a magnetically obstructed f-body are formed. After 7 days of curing ❹m, Lin ㈣ test specimens, tensile strength of 190kg / 0m, no elongation rate, ⑽pull ship, chipping after high impact 驷 / m high impact. In 20 minutes of operation, the gelation and heat generation were unfavorable. The blending amount was 6 kg of epoxy resin and 3 kg of heteroamine compound. The elastic thermosetting composite system of the present invention enables the father-bond bond of epoxy resin and polyamino acid vinegar to form an elastic, adhesive and dynamic composite body, so it is extremely suitable for use in monuments and stone materials. 'Cement materials, magnetic monuments, wood, steel,' junction materials ', stainless steel materials, asbestos boards, gypsum boards, and other construction materials such as adhesion, repair, wiping, etc.' and provide strong dependence, waterproofness, and resistance to acid rain , Impact resistance and beautification effect and other substantial economic benefits. In the present invention, the relevant point measurement is performed with the Cong brush foot—11 VISCOMETER equipment test; the test standards for the mechanical properties of the product refer to the CNS National Standard No. 2 "Ceramic Wall Tablet Adhesive Inspection Method", ", And CNS National Standard No. 1261 丨 "Ceramic Wall Adhesive". Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs // ^ The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

Report A8 B8 C8 D8 0—CH2—CH—CH2 / O '6. Application scope 44672 1 1 · A hardened composite of thermosetting elastic resin, which includes: (a) —General formula (i) means that one molecule contains 15 second Hydroxyl β-group and 1-4 epoxy functional polymers, where R is hydrogen or fluorenyl, and n is 15; CH2-CH-CH2- 0—CH2-CH-CH2- (b) —Molecular composition of 0.1 to 24% by weight of isocyanate-containing residues represented by general formula (2) ', where IT_NC0 isocyanate is 1-3, and R- 0H hydroxyl (please read the notes on the back before filling this page) 1-8, R group is -RC0- II 0 CH2—CH ~ CH3I The type of IT group is -£ CHzCH2CH2CH2〇3- -CH2 ~ CH2—CH2—CH2—CH2—CH2 · ^ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs OMMC I 0 1 R 2 ο c * Λ The paper size is in accordance with the Chinese National Standard (CNS) A4 (ΗΟ × 297mm) < · * ν A8 BS C8 D8 6. The scope of patent application (C) is for compounds of general formula (1) and compounds of general formula (2) The resulting product is modified by grafting, infiltration, reaction, etc. Grafting, racking and other modification effects. The mixing reaction ratio is from 2-200 PHR (combination percentage) of the hydrazone compound, according to the second hydroxyl functional group. Calculate 120-2% of equivalent number, add the product of general formula (2), cross-linking reaction to produce elastic thermosetting composite material of epoxy resin and polyformate, the schematic reaction formula is as general formula (3) In which the activator or catalyst is added to the general formulae (2) and (3) in an amount of 0.01 to 3% by weight, and the type is an organic metal compound containing tertiary amine or tin, lead, mercury, and Cui Gong. _ / 0 \ I OH / ° \ A! 0H Hydroxyl-containing epoxy resin c, please read the precautions on the back before filling this page) Polyacrylic acid activator (c) -► IOICIN, ο- Ministry of Economy Wisdom Printed by National Property Agency Consumer Cooperatives V NICIOL ο This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 2 · Hardening of resins such as those in the scope of patent application a.体 '其 巾 —The general test shown in the general formula 异 contains a lot of different tests ^ containing Wei Wei and the isocyanide-containing energy group = Xingfangxiangyi _ reactant in the presence of activator (Q τ reaction. R— 0Η 十 〇 = C = N—R, mmo ο R—0—C—N—R '(2) 3. If the hardening compound of thermosetting elastic wax is the first item in the scope of patent application, where the general formula (3) Before cross-linking, the product is filled with fillers, modifiers, and rolled to form functional bonding complexes with adjustable functions such as adhesion, waterproofing, impact resistance, and shock resistance. 4. One such as the scope of patent application The method for manufacturing the composite of item 1 is characterized in that it is made of a polyurethane prepolymer in the presence of an activator or a catalyst, and the second hydroxyl group on the epoxy-functional resin is processed at room temperature. Coupling, grafting, reaction. The composition, and the amine-based or cool amine-based compounds are hardened and tightly connected at normal temperature. This paper size is based on China National Standard (CNS) A4 specification (210X297 mm)