TW311920B - - Google Patents

Description

A7 311920 B7 V. Description of the invention () 3 [Scope of invention] (Please read the precautions on the back before filling in this page) This invention is about a kind of rigid polyurethane foam that can be used to produce Adduct of polyalkylene oxide as a polyol and N-aminoethyl hexahydropyridine trap and a method for producing rigid polyurethane foam using the adduct as a part of polyol component . The present invention is particularly concerned with the novel adducts and the use of the adducts as part of the polyol component and the addition of fluorocarbon compounds as blowing agents to replace traditional fluorocarbon compounds (CFC's). Method for preparing hard polyurethane foam with heat resistance and other improved properties. [Explanation of prior art] The rigid polyurethane foam has high thermal insulation and greenness, and also has excellent moldability and processability, so it is widely used in refrigeration equipment, buildings, low temperature, warehouses, storage Tanks, freezing ships or pipe fittings are used as thermal insulation materials. In the production of rigid polyurethane foams by Yingan, a consumer labor cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, a one-step method is usually used, which will consist of polyols, catalysts, foam stabilizers and foaming agents. The components are mixed with the B component mainly composed of organic polyisocyanate to make each component react with each other to simultaneously perform a foaming process and a curing process to form a foam. Among the blowing agents produced by rigid polyurethane foams, the most commonly used is three-gas methane or R-11. Because water reacts with organic polyisocyanates to produce twelve-gas sulfonate gas, water is also used Used as a chemical blowing agent with R-11. The traditional gas-carbon compound taking R-11 as an example is chemically stable, so it diffuses into the stratosphere and breaks the odorous gas layer. As a result, solar ultraviolet rays are not absorbed by the odorous layer and reach the surface of the earth, causing global environmental problems. Therefore. ΓΙ 3 This paper scale is suitable for China National Falcon (CNS) A4 specification (210X 297mm)

311S20 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (4) 1 I The use of oxygen sulfonate compounds has been prohibited or restricted since 1989 > Health 1 1 Polyurethane foam produced The R-11 used is also forbidden or restricted. 0 II In this case, the negative value is near. Many researchers have already produced in-depth research period. Please read first. 1 1 can now replace traditional chlorofluorocarbon compounds or other chlorofluorocarbons The foaming of the master chemical 1 1 agent 0 Some researchers have suggested using water as the only blowing agent instead of R-back 1 1 I 1 1 〇 However,% uses water as the only * — * Cautions for Polyurethane Produced by Foaming Agent I] I ester foam cells contain only digasified sulfonate gas>, and thus the foam has defective items and the thermal insulation of I 〇Another 9 Smok dioxide diffused through the cell wall of the foam body Leakage and the internal pressure of the cell removal decrease with time, so the foam volume shrinkage V, 1 1 | 0 can be the same as ^ xac. Consider increasing the density of the foam to solve this problem * 1 1 | However, its φ iiSLa Non--satisfactory solution 〇1 ί Order 1 On the other hand 9 Hydrogenated fluorosulfon compounds such as dichlorotriethane (HCFC- 1 2 3) or dichloroethane (HCFC-141b) Developed as a substitute for the traditional gas I 1 fluorocarbon compound 0 This substitute or hydrazine fluorosulfonate compound 1 [The odor layer is less destructive 9 However, when considering its main motherhood 9 seems to be almost L impossible. * The actual use is 1 and only the latter may be actually used 0 1 | However > R-11 has a boiling point of 23 V. Vfft and HCFC-141b has a boiling point f of 32¾ of 1 1 so the boiling points of the two blowing agents are very different Big 0 In addition, HCFC two 1 1 141b is used to produce rigid polyurethane Organic polyiso% of ester foams 1 1 Ester or polyol and the final polyurethane foam has greater dissolution 1 | Property I Hard polyamine groups using HCFC -141b as blowing agent The production of formate foam 1 1 body is more rigid than traditional R-11 used as a foaming agent with 1 1 I. For example, the resulting lower fluidity and lower foam size accuracy Question 1 I 1 Question 0 At the same time 1 From the perspective of processing economy Because the price of HCFC -1 4 1 b is expensive 1 1 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 4 (Amendment page) Economy The Ministry of Central Bureau of Pre-Examination and Duty Consumption Cooperation Du Yince A7 B7 Fifth, the invention description () 5 and from the perspective of environmental protection, I hope to reduce the amount of HCFC-14U used as a blowing agent. [Summary of the Invention] Therefore, the purpose of the present invention is to solve the above-mentioned problems and to provide a reoxyxane and N-aminoethylhexahydrogen which can be used as polyols in the manufacture of rigid polyurethane foam The novel adducts of pyrigallium and a method for providing a rigid polyurethane foam using the polyol used as part of this adduct. The specific object of the present invention is to provide a method for producing rigid polyurethane foam, which has high heat resistance and high dimensional stability, and uses the above-mentioned adducts as part of the multi-component Alcohol composition and use should use a smaller amount of a mixture of another chlorine gas master compound and water as a foaming agent to replace the traditional gas gas master compound with R-11 as an example to improve the foaming efficiency. Other improved properties. The present invention provides an adduct of alkylene oxide and N-aminoethyl hexahydropyridine trap with the following formula% / \ > · (Ε0)-(Ρ0) -Η Η- (ΡΟ)-(ΕΟ) -Ν N-CH0CH_N ^ n1 m1

3 3 \ — / \ (E0)-(PO) -H n2 m2 where EO is air-extended ethyl; PO is air-extended propyl; ηι, Π2 and H3 are the average number of air-extended ethyl; 111 + 112 + 113 = 2.0-3.5: mi, ra'2 and m3 are gas (the average number of propyl groups; and πι + πΐ2 + ιη · 3 = 3.0-6.0. (Please read the precautions on the back before filling out this page) 7-Install ---Subscribe I nn HH I — nn nn m ^ i I-In nn · The paper size is applicable to China National Standard (CNS) A4 see grid (210X297mm) 5 A7 311820 B7 5. Description of invention () 6 〔 Brief Description of the Figure] Circle 1 is the infrared absorption spectrum of Polyol A which is an embodiment of the adduct of the present invention; Figure 2 is the proton nuclear magnetic resonance spectrum of Polyol A; Figure 3 is Polyol A III The proton nuclear magnetic resonance spectrum of the gas acetylation product. Figure 4 shows the relationship between the amount of HCFC-141b and the density of the final foam in Example I, Comparative Examples I and II; and Figure 5 shows in the example The relationship between the amount of HCFC-141b and the density of the final foam in II and Comparative Example III. [Detailed description of the invention] It is known that by adding alkylene oxide to have active hydrogen on the molecule The compound used as the starting agent makes an adduct, thereby providing an adduct of cycloalkane. The adduct of cycloalkane and aminoethylhexahydropyridine trap can be prepared in the same way. , By first adding 2.0-3.5 mole φ of ring gas ethane to 1 mole of N-aminoethyl hexahydropyridine trap, thereby forming the gas-extended ethylene represented by E0 in the general formula (I) The average number of Jing gas ethane added to N-aminoethyl hexahydropyrrolidine is represented by Π2 and Π3, and then 3.0-6.0 mole parts of cyclopropane is added to the final of 1 mole part The cyclic gas ethane adduct formed with N-aminoethyl hexahydropyridinium, which forms the gas-propyl group represented by P0 in the general formula (ί), and the group is added to the N-amino group The average number of ring gas propane of ethyl hexahydropyrazine is pseudo-represented by ai, η 2. and ra 3 u _ More specifically, the predetermined amount of ring gas ethane is first in the range of 1 〇〇- 〖2 0 f The i paper f scale is applicable to the standard (CNS) A4 specification (210X297 public broadcasting) (please read the precautions on the back and then fill out this page) Printed by the Ministry of Economic Affairs, Tung Kang Falcon, Unemployed Consumer Cooperative

6 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs-Amendment Date, A7 _ Supplement _ V. Description of invention (7) Reacts with N-aminoethylhexahydropyridine trap at temperature. The reaction is carried out in the absence of a catalyst, however, a catalyst can also be used if necessary. After the Jing gas ethane reaction is completed, then in the presence of potassium hydroxide in the flask in the amount of 0. ΙΟ.4 weight $ based on the weight of the final addition product as a catalyst, in the range of 100-120Ό At a temperature, a predetermined amount of propylene oxide is reacted with the product obtained in the ring gas ethane addition step. The amount of ethylene oxide and cyclopropane reacted with M-aminoethylhexahydropyridine depends on the molecular weight or hydroxyl value of the final addition product, or the target with N-aminoethylhexahydropyridine trap Oxygen extended ethyl / gas extended propyl adduct. After the sequential addition reaction of ring gas ethane and ring gas propane, the reaction product is treated with an acid such as oxalic acid, dilute sulfuric acid or phosphoric acid, or with an alkaline adsorbent such as synthetic silicic acid to make potassium hydrogen in the reaction product Deactivated. Then, the solid matter is removed by filtration and water is removed from the reaction product by using the reaction product under reduced pressure or blowing an inert gas into the reaction product. It is generally advisable to dehydrate the reaction product to a water content of at least 0.10¾. Generally, it is like adding at least about 500 ppm to 100 ppm BHT (2,6-di-third-butyl-4-methylpyridine) to the adduct to stabilize it. The present invention further provides a method for producing a rigid polyurethane foam comprising reacting an organic polyisodonate component with a polyhydric ester in the presence of a foaming agent, wherein the polyhydric alcohol component includes the adducts described above . As shown in 卩. 纟. (: 11 "" 丨 6 "of US Patent No. 3,251,788 is well known in the presence of a blowing agent, the organic polyisocyanate component and the content of polyhydric alcohol component containing cyclopropane and The polyol component of N-aminoethylhexahydropyrrolidine adduct reacts to produce rigid polyurethane foam. This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 public daughter) 7 (Corrected page) --------- f Installed ------ ordered ^ 4 ^ (Please read the notes on the back before filling in this page) 311920 bu η: :: a Ί_I hot object supplement I $ _V. Description of the invention (8) However, the present invention uses the ring gas ethane and propylene oxide in sequence with the H-amino based employee consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs to print the ring compound alcohol. There is no difference in the ability to improve the mixed cipher Yuan into a low-level add-on piece for the magician of chlorine. Each piece of the virginity is changed from the low to the knowledge. The high can be cultivated in the field # 0 耳 ^ Amount of cooked water Some of the characteristics are different from those of pyribene or less than 1 mol. It is obtained by replacing chlorine and qualitatively cultivating temperature, and qualitatively absorbing less hydrogen. It is a system of reducing the ratio of six of Pygolol green hair to _ over two gas fractions, which can be used as hydrogen and an ester to form an effective super-alkane. Alcohols and carbon of the etha # / J body, the base is good, and the base is used to make the gas ❾ of the ττί hydrazine element. Ear, multi-addition atmosphere addition base is changed to amine water N to get it-ethyl hydrogen hydrogen ^ when the addition of externalized amine, and has the ability to get together with the gas hard six gas cultivating another. N-due to the quality, the quality can be obtained. 2. The gas of the ring f. The gas in the base of the ear is inherently hard, the method is hard, and the order of the hydrogen trap is hydrogen. Under the formula, its hexapyridine is added to the 5 'strong base. When the six-use reduction system is used, the anti-inventive substance is in use. The base hydrogen is added to 3. The amine compound makes the ester transfer as a gas-based ester. B-six cultivating enough H-to-B by suitable acid point cyclic control acid goodness by alkanoyl group, pyridyl to glyceryl,, 11 A excellent and easy to change the modified product, promethamine ethyl hydrogen rate plus The knowledge of R-based cultivator's agent R-base shows the amount of oxygen cloth H- The basic effect is six-fold, when the pyridine N-another foam, such as the amine step is more mature than the amine, the ring is sprayed to the amine foam base system, hydrogen and hydrogen. In the case of the first generation, it can be polymerized with sulfide and added with H-fat method. Hexane rate is used as a substitute for quality, and it can be used as a suitable fluoroalkane. It is based on a non-linked base. When it is hard, it can be hardened to obtain a hard amine. Yes. Ear change N-low (please read the precautions on the back before filling in this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm) 8 (Amendment page) Amendment A7 B7 Central Standards of Ministry of Economic Affairs WX printed by the Bureau ’s Consumer Cooperatives: V. Description of the invention (9) N-aminoethyl-JU per mole fraction. When the hydrogen pyridine trap is 3, 0 mole fractions, 0 〒 the adduct has many in-molecules. The residual amine group at the end and the first-stage hydroxyl group f make the reaction difficult to control. However, when spray foaming is performed, the resulting rigid foam can also undergo layer separation. 0 Coking can also occur. 0 When the amount of oxypropane added More than every Molar parts of H-aminoethylhydropyrrolene 6.0 molar parts, the hydroxyl value of the resulting adduct is too low to produce a hard foam with sufficient strength la 〇- The present invention is more suitable for addition The substance is, for example, by first adding 2.5-3.0 mol parts of ethylene oxide to 1 mol part of N-aminoethyl hexahydropyrazine, and then adding 3.5-6.0 mol parts Propylene oxide to 1 mole part of N-aminoethylhydropyrrolidone is prepared to 0 based on the structure> that is, ethylene oxide and epoxy added to N-aminoethylhexahydropyrrolidone The amount of propane 9 adduct has a hydroxyl value of not more than 430 mgKOH / g. Then the 9 adduct preferably has a hydroxyl value of not less than 300 mgi (0H / g. Adducts with a hydroxyl value in the range of 300 to 430 mg Κ0Η / g have an average molecular weight in the range of 35 0 to 561. When the adduct has a hydroxyl value of less than 3 0 0 π g K 0 H / g 9 may often It is not easy to make a rigid polyurethane foam with sufficient strength. It is more suitable to use the adducts in an amount of 1-40 weight percent of the polyol component used. When the polyol component contains less than ίο resuspended amount When it is adducts, it is often not easy to produce rigid polyurethane foams with improved properties in many aspects as mentioned above, and the polyhydric alcohol component contains more than 40 weight S; In the case of > it is often difficult to control the reaction. The polyol component used in the present invention contains an adduct of the first polyol and a second polyol. Any non-adduct polyol can be used as the second polyol --------- ^ Seeds— (please read the precautions on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm) 9 (Amendment page)

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The Ministry of Economic Affairs, Central Bureau of Industry, Beigong Consumer Cooperation Duin 5L A7 B7 V. Description of the invention () 10 However, the second polyol has a hydroxyl value range of 300 to 700 mgKOH / g when the polyol is used in full amount Hydroxyl value. When the polyol component has a hydroxyl value of less than 3 0 0 π! Κ Κ0Η ", it is often difficult to produce a rigid polyurethane foam with sufficient strength. When the polyol component has more than 70 mgK0H / s It is often the case that the resulting rigid polyurethane foam is too brittle and the adhesive strength is also poor. The second polyol is therefore preferably a kind of by adding, for example, ring gas ethane, ring gas propane, ring A polyether polyol made from alkylene oxide of butane or a mixture of these to an organic compound having active hydrogen on the molecule and this second polyol has a hydroxyl value in the range of 300-300ngKOH / g. In the molecule The organic substance with active hydrogen on it may be polyhydric alcohol such as glycerin, tris (hydroxymethyl) propane, pentaerythritol, diglycerol, methylglucoside, sorbitol or sucrose, etc. Functional amines; for example, ortho- or p-toluene diamine aromatic polyfunctional amines; or, for example, tris (hydroxyethyl) amines, alkanolamines. The organic polyisodonate component used in the present invention is preferably Aromatic polyisoradonate. Aromatic polyisoradonate is not particularly limited System, however, the more suitable is polymethyl polyphenyl polyisocyanate, also known as crude MDI, C-MDI or polymer MDI, crude tolylene diisocyanate (TDI), TDI -A prepolymer or a mixture of these. The most suitable is a crude MDI containing polymethyl polyphenyl polyisocyanate in an amount of not less than 70% by weight. The crude MDI may be, for example, Luplanate M20S or Luplanate M-12S (T akeda Bad ische Urethane Kogyo KK), PAP l-1 3 5 (Mitsubishi Chemical Dow), Sumidur 44V-20 or 44V-l〇 (Sumitomo Bayer.) Or Millionate MR-100 or Millionat. This paper ruler and degree are applicable to Chinese national standard Rate (CNS) A4 cash (210X297 mm) 1 〇1-^-it I-ΙΪ (please read the notes on the back before filling this page) T n I n, — = ° line--flflu — ^ m ^ nfl: The Ministry of Economic Affairs, Central Standard Falcon Bureau, Negative Work Consumer Cooperation, Du Printed A7 B7 V. Description of the invention () 11 MR-200 (Nippon Polyurethane KK), etc. The supply of organic polyisofluorate is 85-150 The isocyanate index reacts with the polyol component. The isocyanate index is defined as [the amount of polyisocyanate actually used per meter The resulting amount of polyisogas acid ester that needs to react with the active hydrogen of the hydroxy compound (polyol) and if any water is present] xlOO. Using less than 85 isogas ester index is not easy to form a hard with poor dimensional stability Polyurethane foams, and foams with internal scorch or embrittlement that are not easily obtained with an index of more than 150 isodonate. In the present invention, the other substances and substitutes of the conventional gas-fluoride master compounds of Bu 11 are hydrogenated ammonia-fluoride master compounds or preferably 1 to 2 master alkyls, and the hydrogenated fluoride master compounds are preferably 2 to 4 master compounds. The alkane or gold-fluoride master compound may be 4 to 6 master alkane and all the hydrogens are replaced by amber atoms. These compounds have a low boiling point, that is, they are volatile. Therefore, examples of such substitutes may be, for example, HCFC-141b, HCFC-123 (1, digas-2,2,2-trifluoroethane, with a boiling point of 27.5Ό), HCFC-142bU-chloro-digas Ethane, with a boiling point of-9.71C), 5 HCFC-2 2 (gaseous digas methane, with a boiling point of-4 0.8 t), HCF-1 3 4 a (. 1 -gas-2,2,2 -Trifluoroethane, with a boiling point of 26.3Ό). However, among these compounds, HCFC-141b is the best candidate. Hydrocarbons such as aliphatic or cycloaliphatic hydrocarbons such as n-pentane, pentane, isopentane or mixtures of these can also be used. Dichloromethane can also be used. The amount of substitute used in the present invention can be easily determined by the density ifii of the foam to be produced. For example, relative to 100 parts by weight of the amount of multi-component components used. 10-60 parts by weight of HCFC-141b can be generally used. Μ This paper wave scale is applicable to China National Standard (CNS) Α4 specifications (210X297 mm) ι ι (please read the precautions on the back before filling in this I) Ί outfit ------ ordered ----- (The Ministry of Economic Affairs, Central Bureau of Economic Development, employee cooperation cooperation printed A7 B7 V. Invention description ( ) 12 If HCFC-22 is a gas substitute at normal temperature, it can usually be used in an amount not exceeding 20 parts by weight relative to 100 parts by weight of the polyol used. In the present invention, the substitute is preferably used in combination with water. HCFC-141b is one of the most suitable blowing agents used in the present invention, however, it is more expensive, so on the one hand, the amount of HCFC-141b used should be as small as possible. On the other hand, when the substitute is used with hydration At the time, the foaming reaction proceeded through two gases, HCFC-14 lb and SiO2, to form a cell. After the foaming reaction, the HCFC-14U gas condensed near room temperature, so the internal pressure of the cell fell to a certain level. Degree, while at room temperature or even much lower than room temperature carbon dioxide is still a gas And the pressure drop of the resulting foam through the cell is desirably limited. Generally, the size stability of the rigid foam depends on the backbone structure and the pressure difference between the inside and outside of the cell. Hydration is used as a foaming agent. When the resulting foam is cooled to around room temperature, it will only produce a smaller pressure difference between the inside and outside of the foam than the foam with only the replacement as the foaming agent, because when the replacement condenses The second gasification master in the cell is still gas and therefore the final foam has improved dimensional stability. The replacement and hydration used as a foaming agent then has the advantages of foam properties and processing economy. In the most suitable specific example, based on 100 parts by weight of the polyol component used, HCFC-1 4 1 b in an amount of 15-4 0 parts by weight hydrated with 1.0-3.0 parts by weight of child parts is used. When the amount of water used is less than 1.0 part by weight of the polyol component used relative to 100 parts by weight. The foaming efficiency cannot be significantly improved, but when the amount of water used exceeds the amount of polyol used relative to 100 parts by weight. 3.0 parts by weight of ingredients Due to the two gasification standards, the Chinese national standard falcon (CNS) A4 specification (210X 297 mm) is applicable through the paper wave scale 12 (please read the precautions on the back before filling out this page) -installed ' A7 B7 printed by the Bureau of Consumer Products Co., Ltd. V. Description of the invention () 13 The reverse effect of the size stability of the cell wall to the outside. The polyol component reacts with the organic polyisocyanate component to produce a rigid polyurethane foam It is preferably carried out in the presence of a catalyst or a foam stabilizer. The catalyst used is not limited, and any well-known catalyst can be used. Preferably, the catalyst is an amine catalyst, including, for example, tetramethylhexamethylenediamine (TMHDA, supplied as KAORIZER N0.1 (Kao KK) or TOYOCAT-MR (Toso Κ · K.)), Pentamethyl diethylidene tris Amine (PMDETA, supplied as KA 0 RI ZERH 0.3 (K a ο K. K.) Or T 0 Y 0 CAT-DT (T 〇s ο K · K.)), One of the triethylene diamines Dipropylene glycol solution (usually abbreviated as TEDAL-33, supplied as DABC0-33LV (Air Products)), or bis (2-methylaminoethyl) ether (supplied as TOYOCAT ET (Toso K.K.)). The catalyst can be used alone or in a mixture. Amine catalysts other than those exemplified above or organic gold S compounds can also be used as catalysts if necessary. Especially when spray-foaming to produce rigid foams, such as organometallic compounds of lead octoate and dibutyltin dilaurate. The catalyst is usually used in an amount of 0.01 to 5 wt% based on the polyol used. The foam stabilizer used is not limited, and any foam stabilizer can be used. The foam stabilizer used includes, for example, B-8404, B-8407 or B-8 4 2 5 (supplied by G 〇1 d S ch in idt), F-3 0 5, F-3 4 5 or F-3 7 3 (by

Shin-Etsu Kagaku Kogyo K. K.), SH-19: M by Toray-

Dow Corning), or L-5420, L-5430 or L-5350 (supplied by H ί p p ο n U n i c ar). In addition to the above-mentioned foam stabilizers for manufacturing rigid polyurethane foams, for example, β-80Ι7 can be used (from the paper standard applicable to China National Standards (CNS) Α4 regulation A · (210Χ297mm) 】？ (Please read the precautions on the back before filling in this page) -Binding line 311920 B7

Amend I year month O C? I A 7 to change, # 补 七 i A7 V. Invention description (14)

Gold Schmidt) supplied flexible foam stabilizers for the manufacture of flexible polyurethane foams. Based on the use of polyol ingredients, a foam stabilizer in an amount of 0.5-5 heavy child X can be used. If necessary, any additives such as flame retardants, anti-gasification agents or colorants can be used. For example, it is advisable to use # (gas propyl) phosphate (TCPP) as a flame retardant. When preparing a premix of polyols, a viscosity-reducing agent such as propylene glycolate may also be used if necessary. The rigid polyurethane foam can be prepared by any traditional method. The raw materials shown above were uniformly mixed and the mixture was reacted in a high-pressure foamer. The rigid polyurethane foam of the present invention preferably has a density of about 20-50 kg / ciH3. The present invention will now be described in more detail with reference to examples and reference examples, however, the present invention is not limited to these examples. The materials used in the examples and reference examples are as follows: Polyol A: By first adding 3 mol parts of ring gas ethane to 1 mol parts of N-aminoethylhexahydropyridine, then adding 3.8 mols Parts of propylene oxide to 1 mole parts of H-aminoethyl hexahydropyridine trap adduct, with a flying value of 3 5 3 m gKOH / g, 2900mPa.sec (centipoise) at 25C The viscosity and the content of the first-order hydroxyl group at the end of the molecule are within the scope of the present invention. The size of this paper is applicable to the Chinese National Standard (CNS) A4 (210X297mm) (Please read the precautions on the back before filling this page)

L Printed by the Employees ’Consumer Cooperative of the Central Department of Economics of the Ministry of Economy Γ _______ /, ________ Ϊ ^ i—f nn tm i --- ^^ vm iffn I i ^ J i 1 ^ 1 ^ 1 Year and month, two more * ^ 9 supplement A7 B7 V. Description of invention (15) Printed inferior alcohol B by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs: First add 2.5 mol of ring gas ethane to 1 Mol of N-aminoethyl hydropyrene 9 and then add 3.0 mol of cyclopropane to 1 mol of N-aminoethyl hydropyrene, an adduct prepared by The hydroxyl value of 4 0 5 m gKOH / g, the viscosity at 2 5 1C of 3 5 0 0 m Pa .sec (centipoise), and the content of the primary hydroxyl group at the molecular terminal of 19¾ and the secondary hydroxyl group at the molecular terminal. Within the scope of the invention 〇 Polyol C: by adding 5.8 moles of cyclopropane to 1 moles of amino ethyl_L. Hydrogen pyrazide made of adduct, with 36〇BgKOH / The hydroxyl value of g is 9 55 00 m P a. se C (centipoise) 25 and its viscosity and its molecular terminal Hydroxy-level outside the scope of the present invention 9. More than 7Π alcohol D. By first adding 3.5 mol parts of cyclopropane to 1 mol parts of N-aminoethylhydropyridine t and then adding 2.0 mol parts of ethylene oxide to 1 Molar part of H-aminoethyl—1 ^. Hydropyrazine, with a value of 41 5 mgKOH / s, 3500m Pa • se C (centipoise) viscosity at 251C, 25¾ secondary hydroxyl group at the molecular terminal Content > outside the scope of the present invention 0 more than 7Π alcohol R: by first adding 4.0 pods of ring gas ethane to 1 moles of N-aminoethyl-J * hydropyridine The adduct has a hydroxyl value of 551 mg K 0 H / g of 9 5800 mPa, a viscosity of 25 C at sec (centipoise), and a first-order hydroxyl group at the molecular terminal of 100¾, which is outside the scope of the present invention. The size of this paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) 15 (revision page) -------- ^ installed ------ order ----- Bu A (please read first (Notes on the back and then fill out this page) A7 B7 Printed by the Ministry of Economic Affairs Central Bureau of Industry and Commerce-Cooperatives Co., Ltd. V. Description of invention () 16 Poor alcohol F: prepared by adding a mixture of cyclopropane to M sugar and glycerin The adduct has a diameter value of 450aigK0H / g and a viscosity of 25t at 6000mPa.sec (centipoise). Polyalcohol G: _ An adduct prepared by adding cyclopropane to a mixture of tolylenediamine and tris (hydroxyethyl) amine, has a hydroxyl value of 460mgK0H / s and 5500nPa.sec (Chr) 2 5 t: Lower viscosity. Inferior alcohol H: an adduct prepared by adding 4.0 mole parts of cyclopropane to 1 mole parts of ethylenediamine, having a fly value of 770 mgK0H / g and 250,000 of 50000 mPa.sec (centipoise) υ Lower viscosity. Inferior alcohol Τ: an adduct prepared by adding cyclopropane to the M compound of tolylenediamine and tris (hydroxyethyl) amine, having a hydroxyl value of 455mgK0H / g and 1000 rasPa. Sec (centipoise ) Of 2 5 t: lower viscosity. Shrinkage: CT: emulsification time; the time required for the reaction mixture to become milky after starting to mix materials (seconds) GT: gel time; the time required for the reaction mixture to become viscous and having gel strength after starting to mix materials (Seconds) TMHDA: Tetramethylhexamethylenediamine (amine catalyst) TCPP: Thulium Phosphate (chloropropyl) ester UpUnate M-20S: Polymethyl polyphenyl polyisocyanate with (please read the precautions on the back before filling in (This page) -il ^ i fn i} 'I In n m) ml.

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mu nn irj 4ml ^ nn i 11- 1-— / dm ^ — m ^ —--I —-- I — · 1, ^ im I This paper is used again and again with Chinese National Standard (CNS) A4 specification (210X297 Mm) The Central Falcon Bureau of the Ministry of Economic Affairs printed A7 B7. 5. Description of the invention () 17 180mPa.sec (Lizhi) with a viscosity of 25¾, supplied by Takeda Badische Urethane Kogyo K. K, Millionate MR-100 : Polymethylene polyphenyl polyisogasate, with 25T of 170iaPa.sec (centipoise); lower viscosity, supplied by Nippon Polyurethane KK. The foam body is made by measuring the central part of the foam. Compressive strength: Under 10¾ compression, measure the compressive strength along the direction in which the foam rises. Dimensional stability: After standing at -30t: 24 hours or standing at 50t, 95¾ relative humidity for 24 hours, at Measure the dimensional stability of the foam in a direction parallel or perpendicular to the foaming direction. Polyol / \ 馎 诰 > Gong example An amount of 15 kg of N-aminoethylhexahydropyrrolidine was placed in a pressurizable 70-liter capacity reactor provided with a heating device and a stirring device. After replacing the atmosphere in the reactor with nitrogen, the contents of the reactor were heated to 110 ° C, and then 15.3 kg of ring gas ethane was added continuously over a period of 4 hours. After the addition, the reaction mixture was aged for 1 hour to complete the reaction of ring gas ethane and N-aminoethylhexahydropyridine trap. An amount of 125 ^ potassium hydroxide in the flask was added to the reaction mixture. While maintaining the temperature of the reaction mixture at 1 1 0-1 2 0 t :, 25.6 kg of cyclopropane was continuously added during 4 hours. After addition, the reaction mixture is heated. The paper scale is based on the Chinese National Standard (CNS) A4 specification (210 X 297 mm). Flying 7 ^ Order ^ * Business (please read the precautions on the back and fill in this page) 311820 at B7 The Ministry of Economic Affairs ordered the Central Bureau of Industry and Fisheries to cooperate in the printing of Du. V. Invention description () 18 to 120-130¾ and aging at this temperature for 1 hour to complete the reaction of the propylene oxide institute. A solution of dicrystalline water oxalic acid in an amount of 1 3 0 S was dissolved in 1 liter of water to prepare a solution. This solution was added to the reaction mixture in order to deactivate or neutralize potassium hydroxide, and then the reaction mixture was dehydrated. Polyol A is obtained by squeezing the reaction mixture from the reaction mixture using a filter press to remove the final solid potassium oxalate prepared by the reaction of potassium hydroxide and oxalic acid from the reaction mixture. Yuan Yuan analysis: C Η Ν Measured value 60.43 10.53 8.87 Theoretical value 60.87 10.35 8.73 Theoretical value Burning: Assuming the average number of gas-extended ethyl groups, ηι + η2 + π3 = 3.0 and the average number of oxypropylene groups, mi + m2 + m3 = 3.8 calculated. Infrared Zhumu (TR) spectrum f wave number.em — Π: The first figure shows the infrared absorption spectrum of polyol A; around 11 0 0: -C-0-C-around extension 1500: -CH _fold swing 2800 Near -3000: -C-Η extended Jinzi nuclear magnetic resonance light (NO · PP1B): Figure 2 shows the NMR spectrum of Polyol A; near 1.1: Methyl trivalent protons near 2.5: -NCH2CH2N-based four Near Proton 2.7: The two paper bond scales bonded to 4 (^ 2 (: [{2〇-based nitrogen on methyl are applicable to China National Standards (CNS) A4 specification (210X297mm) 18 (please first Read the precautions on the back and then fill out this page) • Staples' Line Ministry of Economic Affairs Central Falcon Bureau only works with consumers to cooperate with Du Printed A7 B7 V. Description of invention () 19 Protons near 3.1-3.8:-(: 112〇 ~ Two protons of the base are near 3.9 'methine protons

Trifluoroacetic anhydride is used to trifluoroacetate Polyol A to obtain an ester compound. Figure 3 shows the NMR spectrum of the ester compound. g Example T. Comparative Example T Reed T T As shown in Table 1, the foam (free-foamed foam) was prepared by using the materials of the hand and using the free expansion foaming method. Add foam stabilizer, catalyst, flame retardant and foaming agent to 200 parts by weight of polyol component, and adjust the temperature to 20 ± 1TC to prepare polyol premix. The organic polyisocyanate (Luplanate M-20S) was adjusted to a temperature of 20 ± 11C and then added to the polyol premix. After the mixture was stirred for 3 to 5 seconds, it was immediately poured into a 25 cm cubic wooden box in which the separation paper was built to obtain a rigid foam. According to the formulations shown in Tables 2 and 3, rigid foams were prepared in the same manner as above. The reactivity of the material and the properties of the resulting foam are shown in Tables 1 to 3. The fourth letter shows that in Example I and Comparative Examples I I and I I I, H C F C-1 4 1 b uses «to check the density of the obtained foam. When a fixed amount of H C F C-1 4 1 b relative to the polyol component is used, Example I obtains a lower density than Comparative Examples I and I I. If the foaming efficiency remains unchanged regardless of the polyol component used, it should result in a rigid foam with the same foam density. However, as shown in Figure 4, the paper size is applicable to the Chinese National Standard (CNS) 84 specifications (210X297 bumps), (please read the precautions on the back before filling this page) J, -install. Order S11S20 A7 B7 V. Description of the invention () 20 It was found that the density of the sporozoites between the foams produced was different from that of the rhizome, and that the order of the M parts of the ring part was different according to t. , Sixth this gene ethyl amine is not H- and the rate is equivalent to the effect of propylene oxygen hair ring and due to the alkyl lead to the specific bubble. The hair body is obtained by the hair quality. 2) The degree of density is low The comparative example has a better comparison. It is known that cocoa can be transformed into a single alcohol with a large amount of 5 2. In fact, the best place for the specific bubble hair \\ 1 1X scale is better, but it is small, and the body bubble is more dense. 3 melons / 5 k 6 4 2 sexual stability (please read the first (Notes on the back and fill in this education) m nn ml ml ·

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, 1T 17-line Ministry of Economic Affairs Central Bureau of Economic Cooperation and Industry Cooperative Printing and Printing Du ^ i 1 11 nn · This paper size is based on China National Standard (CNS) A4 see grid (2l0X297mm) ο 2 A7 7 Β V. Description of the invention (21) Table 1 Example of du printing by the Ministry of Economy Central Bureau of Accreditation and Consumer Cooperation I 1 2 3 4 5 Raw materials (weight ratio) Polyol A 20 20 20 20 20 Polyol F 40 40 40 40 40 Polyol G 40 40 40 40 40 TCPP 10 10 10 10 10 SH-193 1.5 1.5 1.5 1.5 1.5 Water 2.5 2.5 2.5 2.5 2.5 TMHDA 0.45 0.45 0.45 0.45 0.45 HCFC-141b 17 20 23 26 29 Luplanate M-20S 156 156 156 156 156 Isoarate index 110 110 110 110 110 Reactive CT (sec.) 11 11 11 11 11 GT (sec ·) 51 51 54 58 58 Foam properties Free foam density (kg / m3) 27.4 26.1 24.6 23.6 22.6 Dimensional stability (after standing at -30C for 24 hours) Parallel to the foaming direction U) 0.11 0 0 0.14 Large perpendicular to the foaming direction U) -0.13 -0.13 0 -3.0 Large® shrinkage strength (kg / cm2) (under 10% compression) parallel to the foaming direction U) 1.68 1.62 1.31 1.31 0.17 perpendicular to the foaming direction U) 0.43 0.41 0.3 8 0.31 0.25 This paper uses the Chinese National Standard (CNS) A4 specifications (210X297mm) (please read the precautions on the back before filling this page)

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7 7 AB V. Description of invention () 22 Table 2 Comparative Example I 1 2 3 4 5 Raw materials (weight ratio) Polyol F ~ 50 50 50 50 50 Polyol G 50 50 50 50 50 TCPP 10 10 10 10 10 SH- 193 1.5 1.5 1.5 1.5 1.5 Water 2.5 2.5 2.5 2.5 2.5 TMHDA 2.0 2.0 2.0 2.0 2.0 HCFC-141b 20 23 26 29 32 Lupianate M-20S 162 162 162 162 162 Isocyanate index 110 110 110 no 110 Reactive CT (sec ·) 13 13 13 13 13 GT (sec ·) 50 54 54 56 57 Properties of foams The Ministry of Economy ordered the Central Bureau of Industry and Commerce-Cooperatives to print free foam density (ks / m3) Dimensional stability (-301 After standing for 24 hours) 29.1 27.8 26.4 25.1 24.0 parallel to the foaming direction U) 0 0.18 0.13 greatly perpendicular to the foaming direction (¾) compressive strength (ks / cat2) (under 10¾ compression) 0 -0.13 -0.90 greatly (Parallel to the foaming direction U) 2.22 2.03 1.78 1.55 1.33 Perpendicular to the foaming direction U) 0.59 0.49 0.39 0.32 0.21) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 22 (Please read the back side first Note and then fill in this j)

A7 B7 V. Description of the invention (23) Table 3 Comparative example of Beigong consumer cooperation du printing by the Central Ministry of Economic Affairs of the Ministry of Economic Affairs II 1 2 3 4 5 Raw materials (by weight) Polyol C 20 20 20 20 20 Polyol F 40 40 40 40 40 Polyol G 40 40 40 40 40 TCPP 10 10 10 10 10 SH-193 1.5 1.5 1.5 1.5 1.5 Water 2.5 2.5 2.5 2.5 2.5 TMHDA 0.6 0.6 0.6 0.6 0.6 HCFC-141b 17 20 23 26 29 Luplanate M-20S 156 156 156 156 156 Isocyanate index 110 110 110 110 110 Reactivity CT (sec.) 12 12 12 12 12 GT (sec ·) 47 49 50 52 53 Foam properties Free foam density (kg / m3) 28.4 27.1 25.8 '24.6 23.5 Dimensional stability (after standing at -30Ό after 24 hours) parallel to the foaming direction U) 0 0.15 0.12 0.12 substantially perpendicular to the foaming direction α) 0 -0.14 0 -0.62 large compressive strength (kg / cm2) ( 10% compression) parallel to the foaming direction U) 1.75 1.87 1.55 1.45 1.33 perpendicular to the foaming direction α) 0.56 0.44 0.42 0.33 0.30 The paper size is applicable to China S home standard rate (CNS) A4 specification (210X297 mm)- ------- (-install ------ order ----- ^ 0 (Please read the notes on the back before filling This page) 23 311S20 Attachment Printed by the Employees Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 η Μ-

V. Description of the invention (2 4) Example II, comparative examples III and IV Table I-phases of the same phase by the -ΠΤΤ I Example of applying the foam as shown in the formula to prepare the foam by adding dry bone from the ring The low drop of the alcohol multi-view range is shown in the table 5 as shown in the following. The placement of the ethane ethoxynon bubble is made. In the case of α with If II, the following examples are more specific and higher than the specific temperature. It is clear from the body bubble to the hair that the hair is added to the ethane gas ring. The bubble is only made by the 0 system body. The IV size of the center is safer than that of Biliang. The temperature is high and the application should be high. Wet anti-existent foam materials can be obtained with good results and good alcohol content. Yuan Yingduo can make the control method without the agent, and the difference between the size and the size of the existing size is often not very small. The following paper size applies to the Chinese National Standard (CMS) A4 specification (210X 297mm) 2 4 (Amendment page) (Please read the precautions on the back before filling out this page) A7 B7 5. Description of invention () 25 Table 4 Example II 1 2 3 4 5 Raw materials (weight ratio) Polyol B 20 20 20 20 20 Polyol F 40 40 40 40 40 Polyol G 40 40 40 40 40 TCPP 10 10 10 10 10 SH-193 1.5 1.5 1.5 1.5 1.5 Water 2.5 2.5 2.5 2.5 2.5 TMHDA 0.4 0.4 0.4 0.4 0.4 HCFC-141b 17 20 23 26 29 Lup 1 anate M-20S 159 159 159 159 159 Isocyanate index 110 110 110 110 110 Reactive CT (sec.) 9 9 9 9 9 GT (sec.) 50 50 51 52 52 Foam properties (please read the precautions on the back and then fill in this page) nn n ^ i— mfl flu ^ — {Xiu Xiu < weight 丨 printed by the Male Workers' Consumer Cooperative of the Central Sample Bureau of the Ministry of Economic Affairs Free foam density (ks / ni3) size stability (-30t: after standing for 24 hours) 27.6 26.3 24.8 23.8 22.7 parallel to the foaming direction U) 0.09 0 0 0.14 large perpendicular to the foaming direction U) size Stability (50t :, 95¾ under humidity -0.08 -0.08 0 -0.9 after standing for 24 hours) 0.75 0.80 0.83 0.92 1.01 perpendicular to the foaming direction U) -0.95 -0.96 -1.11 -1.12 -1.19 This paper wave scale is suitable for China National Standard (CNS) A4 Specification (210X 297mm) Month · Year 1

7 7 AB JL'i ^ 11920 V. Description of invention (26) Table 5 Comparative example III Comparative example IV 1 2 3 4 5 1 2 Printed raw materials (weight ratio) of the employee consumer cooperative of the Central Bureau of Samples of the Ministry of Economy Polyol D 20 20 20 20 20 0 0 Polyol E 0 0 0 0 0 20 20 Polyol F 40 40 40 40 40 40 40 Polyol G 40 40 40 40 40 40 40 TCPP 10 10 10 10 10 10 10 SH-193 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Water 2.5 2.5 2.5 2.5 2.5 2.5 2.5 TMHDA 0.6 0.6 0.6 0.6 0.6 0.1 0.1 HCFC-141b 17 20 23 26 29 17 '20 Luplanate H-20S 159 159 159 159 159 167 167 Isoester Index 110 110 110 110 110 110 110 Reactive CT (sec.) 9 9 9 9 9 8 8 GT (sec ·) 46 48 49 · 52 52 27 30 Foam properties Free foaming density (kg / n3) Size stability 29.0 27.6 26.1 24.8 23.5 25.1 23.5 (after standing at -30¾ for 24 hours) parallel to the foaming direction (50 0 0 0 0 large 0.14 large perpendicular to the foaming direction (¾) Dimensional stability 0 0 -0.15 -0.17 large -0.57 large (5〇υ, 95¾ after 24 hours under humidity) 1 1.19 1.07 1.21 1.22 1.14 greatly perpendicular to the foaming direction (¾) -1.45 -1.43 -2.45 -2.09 -2.36 Great (please read the precautions on the back before filling in this page) This paper wave scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 26 (revision page) A7 B7 Description of the invention (2 7) ILiL .... M-Ι IL is prepared according to the following formula. This premix has a viscosity of 8 5 nPa.sec (centipoise) measured at 25 C. Polyol A 30 Weight parts Polyol Η 40 Polyol I 30 TCPP 15 SH-193 1.5 Water 1.0 TEDA L-33 2.0 Lead octoate (2050 0. 3 HCFC- 1 41 b 50 (Please read the precautions on the back before filling this page)- -Installation ---- The premix and Mlllionate MR-100 printed by the Pinggongxiao F Cooperative of the Central Bureau of Economic Development of the Ministry of Economic Affairs are mixed with each other in the same volume and the mixture is sprayed and foamed with a spray foaming machine On 5mm thick plywood. It was found that the resulting foam had the following excellent appearance and properties. The sacks had no layer separation or cracking. -▲-This paper wave scale is easy to use Chinese National Standard (CNS) A4 specification (210X297mm) 28 A7 B7 5. Description of the invention (The number of layers of foam The density of foam density size stability (-30Ό x24h " s) parallel to the foaming direction-perpendicular to the foaming direction-viscous strength thermal conductivity flammability (J IS A-9512) 3 layers 30.0kg / m3 0.37¾ 0.22¾ 2 .56 kg / cm3 (foam壊 壊) 0.0160 Kcal / m.hr.t; can be annoying (4 0 sec, 3 7 m hi) -------- installed-(please read the precautions on the back before filling this page) Order- ----- ^ V, the paper printed by the Ministry of Economic Affairs of the Central Committee of the Ministry of Economic Affairs and Consumer Cooperatives of the paper standard is applicable to China National Standards (CNS) A4 specifications (210X297 mm)

Claims (1)

Ο 2 S 1 s Annex III Η Amendment of the patent scope of Patent Application No. 83107042 printed by the Employee Welfare Committee of the Central Standards Bureau of the Ministry of Economic Affairs (October 29, 85) 1. A method for manufacturing a rigid polyurethane foam, including foam In the presence of an agent, the organic polyisocyanate component is reacted with a multicomponent component, wherein the polyhydric alcohol component includes the adduct of cycloalkane and N-aminoethylhexahydropyridinium with the formula / ~ \ / (EO )-(PO) -H H- (PO)-(EO) -N N-CH CH_N ^ Π1 mi m3 n3 \ __ / 2 2 '(EO)-(PO) -H n2 m2 where EO is air stretch B Base, PO is air-extended propyl; ni, n2 and n3 are the average number of air-extended ethyl; 111 + 112 + 113 =: 2.0-3.5: mi, m2 and m3 are the average number of air-extended propyl; and bi + bi2 + b3 = 3.0-6.0. 2. The method as claimed in item 1 of the patent application scope, in which the adduct has a flying value of 300 to 430 mgK0H / g. 3. For example, the preparation method of the first item in the scope of patent application, in which the polyol component contains an adduct in an amount of 10-40% by weight. 4. For the method of patent application, the polyol component has a warp value of 300 to 700 agiC0H / g. 5. The method as claimed in item 1 of the patent application, wherein the blowing agent is like at least one other gaseous fluorosulfonate compound selected from the group consisting of argon gas fluorine master compounds, hydrogenated fluorocarbon compounds and perfluoro master compounds. 6. For example, the manufacturing method of item 1 of the patent application scope, in which the blowing agent is a mixture of water and at least one other gaseous fluorine master compound, the other gaseous fluorine sulfonate paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 gold) 1 H3 compounds are proudly selected from the group consisting of hydrogenated gas carbon compounds, hydrogenated fluorosulfon compounds and total gas sulfon compounds. ?. For example, the manufacturing method of item 1 of the patent application scope, in which the blowing agent is 1,1-digas -1 -fluoroethane. 8. As in the preparation method of item 1 of the patent application scope, the blowing agent is a mixture of water and 1,1-dichloro-1-fluoroethane. 9. For the manufacturing method of item 1 of the patent application scope, 15-40 parts by weight of 1,1-digas-1-fluoroethane and 1.0-3.0 parts by weight of water are used with respect to 100 parts by weight of the polyol component As a foaming agent. 10. As in the preparation method of the first item of patent application, the polyisodonate component is polymethylidene polyphenyl polyisocyanate. 11. A rigid polyurethane foam, a rigid polyurethane foam prepared by reacting an organic polyisocyanate component with a polyol component in the presence of a blowing agent, The polyol component includes the adduct N-CH-CH-N. 1 '/ 2 2 \ (Ε〇)-(ρ〇) of alkylene oxide having the formula -η H- (P〇) m3- (EO) n ^ (EO)-(PO) Ή The Employee Welfare Committee of the Central Bureau of Standards of the Ministry of Economic Affairs printed a base B stretch of ο in which the base B stretch is 3 π and 2 η; the number of flat and average base propylene stretching oxygen is S3 and η + + 1 and the size of this paper are applicable to China National Standards (CNS) A4 specifications (210 X 297 public director) 2